US9563075B2 - Method for manufacturing liquid crystal display device provided with front plate, and liquid crystal display device provided with front plate - Google Patents
Method for manufacturing liquid crystal display device provided with front plate, and liquid crystal display device provided with front plate Download PDFInfo
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- US9563075B2 US9563075B2 US13/882,903 US201113882903A US9563075B2 US 9563075 B2 US9563075 B2 US 9563075B2 US 201113882903 A US201113882903 A US 201113882903A US 9563075 B2 US9563075 B2 US 9563075B2
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Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/035—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
- G02F1/133331—Cover glasses
-
- G02F2001/133331—
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/40—Materials having a particular birefringence, retardation
-
- Y10T428/1036—
-
- Y10T428/105—
-
- Y10T428/1059—
Definitions
- the present invention relates to a method for manufacturing a liquid crystal display device with front plate and to a liquid crystal display device with front plate.
- a sealing layer which fills the void for bringing the front plate and the liquid crystal panel into close contact.
- the most suitable method is ultraviolet curing using ultraviolet curable resin as the sealing layer.
- patent literature 1 discloses a technique of avoiding deterioration of display quality without damaging a liquid crystal panel by irradiating the photocurable resin only with light at a wavelength of 340 nm or more and blocking light at a wavelength less than 340 nm, which has a negative influence on liquid crystal molecules, adhesives and the like.
- a preferable method is providing a sealing layer containing an ultraviolet curing sticking agent, a front plate composed of glass or an acrylic resin, an adhesive layer, and a resin film having a hard coat layer in this order on the surface on the viewing side of a liquid crystal panel which has polarizing plates on both faces of the liquid crystal cell, followed by irradiation with ultraviolet ray from the hard coat layer side so as to cure the sealing layer.
- PC film polycarbonate films
- PET films polyethylene terephthalate films
- cellulose acylate films and the like are in practical use.
- PC films polycarbonate films
- PET film polyethylene terephthalate films
- PET film polyethylene terephthalate films
- triacetylcellulose films having hard coat layer, which have conventionally been used for polarizing plates and liquid crystal display devices, are advantageous as a hard coat film to be pasted on a front plate, because TAC films do not cause moire by their low phase difference and thus have high transparency and good processability.
- TAC films do not cause moire by their low phase difference and thus have high transparency and good processability.
- an ultraviolet absorber contained in the TAC film absorbs the ultraviolet ray for curing the sealing layer. The amount of the ultraviolet ray is thus decreased before reaching the sealing layer, and the sealing layer cannot be cured sufficiently. Therefore, decrease in contrast is caused by delamination or distortion between the liquid crystal panel and front plate.
- the TAC film with a hard coat layer is subjected to heat and the ultraviolet ray itself. It causes wrinkles or distortion between the hard coat layer and the base film and delamination of the hard coat layer, which have been another problem.
- an object of the present invention is to provide a method for manufacturing a liquid crystal display device with a front plate having high contrast and high visibility, including bringing a front plate into close contact with a liquid crystal panel via a sealing layer including an ultraviolet curing sticking agent, the front plate being applied with a base film where an adhesion improver containing resin layer and a hard coat layer are provided on the surface of the base film in this order, wherein the sealing layer can be sufficiently cured by ultraviolet ray while the cellulose acylate film does not develop wrinkles or distortion between the hard coat layer and the base film or delamination of the hard coat by the ultraviolet ray.
- a method for manufacturing a liquid crystal display device with a front plate including:
- a sealing layer including at least an ultraviolet curing sticking agent, a front plate composed of glass or an acrylic resin, an adhesive layer, and a base film where an adhesion improver containing resin layer and a hard coat layer are provided on a film surface of the base film in this order, in a manner that the hard coat layer is on a topmost surface;
- the adhesion improver containing resin layer includes a compound having an absorption maximum peak ( ⁇ max) in a wavelength range of 260 to 400 nm as an adhesion improver in an amount of 0.005 to 0.5 parts by mass with respect to 100 parts by mass of a binder resin of the adhesion improver containing resin layer.
- ⁇ max absorption maximum peak
- the base film on which the adhesion improver containing resin layer is provided has a light transmittance at 380 nm wavelength of 51% or more.
- the compound having an absorption maximum peak ( ⁇ max) at the wavelength range of 260 to 400 nm is a benzotriazol-based compound or a benzophenone-based compound.
- nx, ny and nz are refractive indexes in a condition of 23° C., 55% RH and 590 nm wavelength; nx represents a maximum refractive index in a film plane or called refractive index in a slow axis direction; ny represents a refractive index in a direction perpendicular to the slow axis in the film plane; nz represents a refractive index of the film in a thickness direction; and d represents a film thickness (nm)).
- a liquid crystal display device with a front plate manufactured by the method for manufacturing a liquid crystal display device with a front plate of any one of the above 1 to 4.
- liquid crystal display device with a front plate is a liquid crystal display device for a stereoscopic image.
- a method for manufacturing a liquid crystal display device with a front plate having high contrast and high visibility including bringing a front plate into close contact with a liquid crystal panel via a sealing layer including an ultraviolet curing sticking agent, the front plate including a base film which is pasted on a surface and on which an adhesion improver containing resin layer and a hard coat layer are provided in this order, wherein the sealing layer can be sufficiently cured by ultraviolet ray while the base film does not develop wrinkles or distortion between the hard coat layer and the base film or delamination of the hard coat layer by the ultraviolet ray.
- FIG. 1 This is a schematic diagram of a method for manufacturing a liquid crystal display device with a front plate according to the present invention.
- FIG. 2 This is a schematic diagram showing a co-film casting die forming a multi-layered web film casting.
- a method for manufacturing a liquid crystal display device with a front plate includes:
- a sealing layer including at least an ultraviolet curing sticking agent, a front plate composed of glass or an acrylic resin, an adhesive layer, and a base film where an adhesion improver containing resin layer and a hard coat layer are provided on a film surface of the base film in this order, in a manner that the hard coat layer is on a topmost surface;
- the adhesion improver containing resin layer includes a compound having an absorption maximum peak ( ⁇ max) in a wavelength range of 260 to 400 nm as an adhesion improver in an amount of 0.005 to 0.5 parts by mass with respect to 100 parts by mass of a binder resin of the adhesion improver containing resin layer.
- ⁇ max absorption maximum peak
- FIG. 1 is a schematic diagram of the method for manufacturing the liquid crystal display device with a front plate of the present invention.
- FIG. 1 shows a minimum configuration of the method for manufacturing the liquid crystal display device with a front plate of the present invention, and the present invention is not limited thereto.
- a sealing layer 3 including an ultraviolet curing sticking agent, a glass or acrylic front plate 4 , an adhesive layer 5 and a base film 6 including an adhesion improver containing resin layer 7 and a hard coat layer 8 are laid in this order where the hard coat layer is the topmost surface. They are irradiated with ultraviolet ray from the hard coat layer side so that the sealing layer 3 is cured to bring the liquid crystal panel into close contact with the front plate.
- the present inventors experimentally made a hard coat film in which an ultraviolet absorber was simply removed from a conventional base film with a hard coat layer so that it did not prevent the sealing layer including the ultraviolet curing sticking agent from photo-curing by the ultraviolet ray. Ultraviolet irradiation was applied to cure the sealing layer, and a liquid crystal display device with a front plate was thus prepared. The present inventor then found that if the amount of ultraviolet irradiation was regulated to be within the range sufficient to cure the sealing layer, it caused the hard coat film wrinkles or distortion between the hard coat layer and the base film or delamination of the hard coat layer as well as uneven contrast of the liquid crystal imaging, which were problematic in practical use.
- the adhesion improver containing resin layer 7 contains a compound having an absorption maximum peak ( ⁇ max) at a wavelength of 260 to 400 nm as an adhesion improver in an amount of 0.005 to 0.5 parts by mass with respect to 100 parts by mass of a binder resin of the adhesion improver containing resin layer, it greatly improves the wrinkles and distortion between the hard coat layer and the base film and delamination of the hard coat layer.
- ⁇ max absorption maximum peak
- the base film which is provided with the adhesion improver containing resin layer of the present invention has a light transmittance at 380 nm wavelength of 51% or more.
- curing the sealing layer can be compatible with providing the hard coat film having no wrinkle and distortion between the hard coat layer and the base film and no delamination of the hard coat layer.
- the compound of the present invention having an absorption peak ( ⁇ max) at a wavelength of 260 to 400 nm is a benzotriazole-based compound or benzophenone-based compound.
- the adhesion improver containing resin layer is provided in which the amount of the compound of the adhesion improver is adjusted within a specific range, it absorbs a moderate amount of the ultraviolet ray which the sealing layer is supposed to be irradiated with and produces heat. The heat then diffuses and thus makes the adhesion between the base film surface and the resin of the hard coat layer in the hard coat film stronger.
- the ultraviolet irradiation causes wrinkles or distortion between the hard coat layer and the base film or delamination of the hard coat layer as in the case where the ultraviolet absorber is simply removed from the base film. If the amount of the compound is over 0.5 parts by mass, excessive heat is produced to cause larger distortion between the hard coat layer and the base film or bleed out to deteriorate the adhesiveness.
- the influence of the heat which the adhesion improver produces when irradiated with the ultraviolet ray can be limited compared to the case where the compound is contained in the film or hard coat layer. In addition, it can be prevented that interaction with other additive components causes deterioration or bleed out.
- the liquid crystal panel of the present invention includes the polarizing plates 1 and 1 a on both faces of the liquid crystal cell 2 .
- the polarizing plates may be the same or different.
- the liquid crystal cell 2 may be any of reflective, transflective and transmissive LCDs, and LCDs of various types such as TN, STN, OCB, HAN, VA (PVA, MVA) and IPS are preferably used.
- the polarizing plates 1 and 1 a of the present invention is a stretched polyvinyl alcohol doped with iodine or dichromatic dye as a polarizer, in which a polarizing plate protective film supports at least one face of the polarizer.
- the polarizer has a film thickness of 5 to 40 ⁇ m, preferably 5 to 30 ⁇ m, particularly 5 to 20 ⁇ m.
- the above polarizing plate protective film is not particularly limited, but is preferably a polymer film. It is preferable that the protective film is easily produced, optically uniform and optically transparent. As long as having these properties, the protective film may be any film such as cellulose acylate-based film, polyester-based film, polycarbonate-based film, polyarylate-based film, polysulfone (including polyethersulfone)-based film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylenevinyl alcohol film, syndiotactic polystyrene-based film, polycarbonate film, norbornene resin-based film, polymethylpentene film, polyether ketone film, polyether ketone imide film, polyamide film, fluorine-containing resin film, nylon film, cyclo
- These films are preferably manufactured by solution film casting or melt casting.
- cellulose acylate film, polycarbonate film, polysulfone (including polyethersulfone), cycloolefin polymer film are preferable.
- cellulose acylate film and cycloolefin polymer film are particularly preferable in terms of production, cost, transparency, uniformity, adhesiveness and the like.
- KONICA MINOLTA TAC KCSUX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC16UR, KC4UE, KC8UE, KC4FR-1 and KC4FR-2 are commercially available cellulose acylate films which are preferably used.
- ZEONOR Zero Corp.
- ZEONOR is a commercially available cycloolefin polymer film which is preferably used,
- the polarizing plates may be manufactured by a general method. It is preferable that alkali-saponified protective films are pasted onto both faces of the polarizing plate with an aqueous solution of completely saponified polyvinylalcohol.
- the liquid crystal panel of the present invention may be used for a stereoscopic image display device.
- the stereoscopic image display device is composed of the liquid crystal panel and liquid crystal shutter glasses.
- the liquid crystal shutter glasses may be composed of (1) a protective film, liquid crystal cell and polarizer in this order, or (2) a protective film, polarizer, liquid crystal cell and polarizer in this order.
- the liquid crystal panel alternately displays right-eye images and left-eye images, which are stereoscopic disparity images of an object, and the liquid crystal shutter glasses distributes the images to right and left eyes respectively to visualize stereoscopic images.
- the base film with the hard coat layer which is pasted on the front plate, does not have phase difference.
- the retardation Ro in the in-plane direction represented by the following equation is 0 to 5 nm and the retardation Rth in the thickness direction represented by the following equation is ⁇ 10 to 10 nm.
- Ro ( nx ⁇ ny ) ⁇ d Equation (i)
- R th ⁇ ( nx+ny )/2 ⁇ nz ⁇ d Equation (ii)
- nx, ny and nz are refractive indexes in the condition of 23° C., 55% RH and 590 nm, where nx represents the maximum refractive index in the film plane (also called refractive index in the slow axis direction); ny represents the refractive index in the direction perpendicular to the slow axis in the film plane; nz represents the refractive index of the film in the thickness direction; and d is the film thickness (nm).
- the above retardations can be determined by the measurement with an automatic birefringence meter KOBERA-21ADH (Oji Scientific Instruments Co.) in the environment of 23° C. and 55% RH at a wavelength of 590 nm.
- KOBERA-21ADH Oji Scientific Instruments Co.
- the base film having little phase difference as described above can be obtained by adding the polymer described below.
- the sealing layer 3 of the present invention is a sealing layer containing the ultraviolet curing sticking agent and is cured by ultraviolet irradiation to bring the liquid crystal panel into close contact with the front plate.
- the ultraviolet curing sticking agent includes an ultraviolet curing component and a photopolymerization initiator, and if necessary, further includes a commonly used additive such as a cross-linker, tackifier, filler, anti-aging agent or coloring agent.
- the ultraviolet curing component may be any monomer, dimer, oligomer or polymer which has a carbon-to-carbon double bond in the molecule and is curable by radical polymerization.
- examples thereof include, for example, esters of (meth)acrylic acid and polyol such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tetraethyleneglycol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, neopentylglycol di(meth)acrylate and dipentaerythritol hexa(meth)acrylate; ester acrylate oligomers, and isocyanurates or isocyanurate compounds such as 2-propenyl-di-3-butenylcyanurate, 2-hydroxyethyl-bis(2-acryloxyethyl)isocyanurate, tris(2-methacrylaoxyethyl
- a photoelastic resin “SVR” produced by Sony Chemical & Information Device Corp, which is mainly composed of acrylic-based ultraviolet curing resin, and the like is a suitable commercially available ultraviolet curing component.
- the present invention is not limited by a specific ultraviolet curing component, and various curing components may be used as long as they are not apart from the technical idea of the present invention and they are curable by ultraviolet ray in terms of simplicity of manufacturing.
- the photopolymerization initiator may be any substance which is cleaved by ultraviolet ray of the wavelength triggering the polymerization reaction so as to produce a radical.
- examples include, for example, benzoinalkylethers such as benzoinmethylether, benzoinisopropylether and benzoinisobutylether; aromatic ketones such as benzyl-, benzoyl-, benzophene- and ⁇ -hydroxycyclohexyl phenylketone, aromatic ketals such as benzyldimethylketal; polyvinylbenzophenone; thioxanthones such as chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone and diethylthioxanthone.
- examples of the cross-linker include, for example, polyisocyatate compounds, melamine resin, urea resin, polyamine, carboxyl group containing polymer and the like.
- the sticking agents may be solvent, emulsion, hot-melt or the like, and forms of solvent or emulsion are generally used.
- the sticking agents may be prepared in the form of coating liquid by adding other auxiliary agents.
- the other auxiliary agents may include viscosity depressants, thickeners, pH adjusters, defoamers, preservatives and antifungal agents, pigments, inorganic fillers, stabilizers, wetting agents, moisturizers and the like.
- the sealing layer may be formed by applying a coating composition of the sealing layer using a known method such as gravure coating, dip coating, reverse coating, wire bar coating, die coating and inkjet, followed by subsequent heating and drying, and curing by ultraviolet ray.
- a coating composition of the sealing layer using a known method such as gravure coating, dip coating, reverse coating, wire bar coating, die coating and inkjet, followed by subsequent heating and drying, and curing by ultraviolet ray.
- the sealing layer has an average dry film thickness of 0.1 to 50 ⁇ m, preferably 1 to 40 ⁇ m, particularly 10 to 30 ⁇ m.
- the light source for the ultraviolet curing may be any ultraviolet emitting light source.
- a low-pressure mercury lamp, middle-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp or the like may be used.
- ultraviolet irradiation dose is normally 1,000 to 6,000 mJ/cm 2 in terms of integral of light, and preferably 2,000 to 5,000 mJ/cm 2 .
- the front plate 4 is required to be transparent, flat and physically strong.
- the front plate 4 is formed using glass, acrylic resin or the like.
- the adhesive layer 5 of the present invention is a layer containing a sticking agent (including adhesive) which bonds the front plate and the base film with the hard coat layer of the present invention together.
- the sticking agent may be any pressure sensitive agent such as rubber-based sticking agent, acrylic sticking agent and silicone-based sticking agent.
- an acrylic sticking agent is used because it is clear and colorless and has good adhesiveness to a liquid crystal cell. It is preferable that the acrylic sticking agent has a weight average molecular weight of a base polymer of 300,000 to 2,500,000 or around.
- the monomer of an acrylic polymer which is the base polymer of the acrylic sticking agent may be various types of alkyl (meth)acrylate, (where alkyl (meth)acrylate represents alkyl acrylate and/or alkyl methacrylate, and (meth) means the same in the following).
- alkyl (meth)acrylate include, for example, methyl (meth)acrylate, ethyl (meth acrylate, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. These alkyl (meth)acrylates may be used alone or in combination.
- (meth)acrylic acid, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-methylol (meth)acylamide or the like may also be used in place of a part of alkyl (meth)acrylate.
- other co-polymerizable monomers such as vinyl acetate and styrene may be used together as desired to the extent that the acrylic polymer does not lose its sticking properties.
- the acrylic polymer may be manufactured by various known methods, for example, by radical polymerization such as bulk polymerization, solution polymerization and suspension polymerization as needed.
- the radical polymerization initiator may be of various known types such as azo-based compounds and peroxide-based compounds.
- solution polymerization is preferable, where polar solvent such as ethyl acetate or toluene is generally used as the solvent of the acrylic polymer.
- the base polymer of the rubber-based sticking agent may be, for example, natural rubber, isoprene-based rubber, styrene-butadiene-based rubber, reclaimed rubber, polyisobutylene-based rubber, and may further bestyrene-isoprene-styrene-based rubber, and styrene-butadiene-styrene-based rubber and the like.
- the base polymer of the silicone sticking agent may be, for example, dimethylpolysiloxane, diphenylpolysiloxane and the like.
- the sticking agent preferably contains a cross-linker.
- the cross-linker include polyisocyanate compounds, polyamine compounds, melamine resin, urea resin, epoxy resin, metal chelates and the like.
- the sticking agent may be used with as necessary a tackifier, plasticizer, filler, antioxidant, ultraviolet absorber, silane coupling agent and the like to the extent not being apart from the object of the present invention.
- the thickness (dry thickness) of the sticking agent layer is thinner, and specifically 5 to 30 ⁇ m or around.
- the adhesion improver containing resin layer of the present invention is provided between the base film and the hard coat layer.
- the adhesion improver containing resin layer of the present invention characteristically contains a compound (hereinafter referred to as an adhesion improver) having an absorption maximum peak ( ⁇ max) in a wavelength range of 260 to 400 nm as the adhesion improver in an amount of 0.005 to 0.5 parts by mass with respect to 100 parts by mass of a binder resin of the adhesion improver containing resin layer.
- an adhesion improver a compound having an absorption maximum peak ( ⁇ max) in a wavelength range of 260 to 400 nm as the adhesion improver in an amount of 0.005 to 0.5 parts by mass with respect to 100 parts by mass of a binder resin of the adhesion improver containing resin layer.
- the adhesion improver is contained in such an amount that it does not affect the amount of ultraviolet irradiation to the sealing layer while the hard coat film does not develop wrinkles or distortion between the hard coat layer and the base film or delamination of the hard coat layer. It is more preferable that the content is 0.005 to 0.1 part by mass with respect to 100 parts by mass of the binder resin.
- the base film which is provided with the adhesion improver containing resin layer has a light transmittance at 380 nm wavelength of preferably 30% or more, more preferably 51% or more, and particularly 70% or more.
- the adhesion improver is a compound having an absorption maximum peak ( ⁇ max) in a wavelength range of 260 to 400 nm
- a suitable solvent e.g., dichloromethane or toluene
- a spectrophotometer UVIDFC-610 by Shimadzu Corp.
- self-recording spectrophotometer model 330 self-recording spectrophotometer model U-3210
- self-recording spectrophotometer model U-3410 self-recording spectrophotometer model U-4000 by Hitachi Corp. or the like.
- adhesion improver of the present invention examples include, for example, oxybenzophenone-based compound, benzotriazole-based compound, salicylate ester-based compound, benzophenone-based compound, cyanoacrylate-based compound, nickel complex salt-based compound and triazine-based compound.
- oxybenzophenone-based compound benzotriazole-based compound
- salicylate ester-based compound benzophenone-based compound
- cyanoacrylate-based compound nickel complex salt-based compound and triazine-based compound.
- nickel complex salt-based compound and triazine-based compound examples include, for example, oxybenzophenone-based compound, benzotriazole-based compound, salicylate ester-based compound, benzophenone-based compound, cyanoacrylate-based compound, nickel complex salt-based compound and triazine-based compound.
- benzotriazol-based compounds, benzophenone-based compounds and triazine-based compounds are preferable because these compounds cause little coloration
- the adhesion improver has good absorbance of ultraviolet ray at a wavelength of 370 nm or less as well as little absorbance of visible light at a wavelength of 400 nm or more in terms of liquid crystal display properties.
- the adhesion improver has an absorption maximum in a wavelength range of 260 nm to 355 nm because such adhesion improver has better adhesion improving effect per ultraviolet irradiation dose.
- benzotriazol-based compounds of the present invention are compounds represented by the following general formula (A).
- R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different, each of which independently represents a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxy group, acyloxy group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or heterocyclic group of 5 or 6 members, and R 4 and R 5 may cyclize to form a carbon ring of 5 or 6 members.
- Useful benzotriazol-1-based compounds for the present invention include 2-(2′-hydroxy-5′-methylphenyl)benzotriazol, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazol, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)benzotriazol, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazol, 2-(2′-hydroxy-3′-(3′′,4′′,5′′,6′′-tetrahydrophthalimidemethyl)-5′-methylphenyl)benzotriazol, 2,2-methylene-bis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phen) 2-(2-hydroxy-3′-tert-butyl-5-methylphenyl)-5-chlorobenzotriazol, 2-(2H
- benzophenone-based compounds of the present invention are compounds represented by the following general formula (B).
- Y represents a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group or phenyl group, where alkyl, alkenyl and pheynyl group may have substituent(s);
- A represents a hydrogen atom, alkyl group, alkenyl group, phenyl group, cycloalkyl group, alkylcarbonyl group, alkylsulfonyl group or —CO(NH)n-1-D group where D represents an alkyl group alkenyl group or a phenyl group with or without substituent(s); and m and n each represent 1 or 2.
- the alkyl group represents a linear or branched aliphatic group having up to 24 carbon atoms
- the alcoxy group represents an alcoxy group of up to 18 carbon atoms
- the alkenyl group represents an alkenyl group of up to 16 carbon atoms such as ally, group and 2-butenyl group.
- substituent of the alkyl, alkenyl and phenyl group include halogen atoms such as chlorine, bromine and fluorine atoms, hydroxyl group, phenyl group (this phenyl group may have substituent(s) such as alkyl group or halogen atom) and the like.
- benzophenone-based compounds represented by the general formula (B) will be listed below, but not limited thereto.
- Examples include, for example, 2,4-dihydzroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenylmethane) and the like.
- CHIMASSORB 81 (BASF Japan Ltd.) is preferably used.
- the binder resin used in the adhesion improver containing resin layer of the present invention is preferably a thermoplastic resin or active ray (e.g. ultraviolet ray) curing resin, and is applied in the form of solution dissolved in a suitable solvent.
- a thermoplastic resin or active ray e.g. ultraviolet ray
- the thermoplastic resin may be, for example, cellulose acylates such as cellulose diacetate, cellulose triacetate, cellulose acetatebutylate, cellulose acetatephthalate, cellulose acetatepropionate and cellulose nitrate, polyesters such as polyvinyl acetate, polystyrene, polycarbonate, polybutylene terephthalate and copolybutylene tere/iso-phthalate, polyvinylalcohol derivatives such as polyvinylalcohol, polyvinylformal, polyvinylacetal, polyvinylbutyral and polyvinylbenzal, norbornene-based polymers having a norbornene compound; and acrylic resins such as copolymers including methyl methacrylate, e.g., polymethylmethacry late, but not particularly limited thereto.
- cellulose acylates such as cellulose diacetate, cellulose triacetate, cellulose acetatebutylate, cellulose acetatephthalate,
- Active ray curing resin is a resin which is curable by cross-linking reaction or the like by active ray irradiation such as ultraviolet ray or electron beam.
- Representative examples of the active ray curing resin include ultraviolet curing resins and electron beam curing resins, and may also include other resins which are curable by active ray irradiation besides ultraviolet ray and electron beam.
- Examples of the ultraviolet curing resin include, for example, ultraviolet curing acrylic urethane-based resin, ultraviolet curing polyester acrylate-based resin, ultraviolet curing epoxy acrylate-based resin, ultraviolet curing polyol acrylate-based resin, ultraviolet curing epoxy resin and the like.
- an ultraviolet curing acrylic urethane-based resin can be obtained easily by such a way that a polyester polyol is reacted with an isocyanate monomer or prepolymer, and the obtained product is further reacted with an acrylate-based monomer having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter, “acrylate” will be defined to include methacrylate, even if simply denoted as “acrylate”) or 2-hydroxypropyl acrylate (see Japanese Patent Application Laid-Open Publication No. Sho59-151110, for example).
- an ultraviolet curing polyester acrylate-based resin can be obtained easily by such a way that a polyester polyol is reacted with an acrylate-based monomer such as 2-hydroxyethyl acrylate or 2-hydroxy acrylate (see Japanese Patent Application Laid-Open Publication No. Sho59-151112, for example).
- ultraviolet curing epoxy acrylate-based resin examples include compounds obtained in such a way that an epoxy acrylate is reacted to be an oligomer, and is further reacted by adding a reactive solvent and photoreaction initiator thereto (see Japanese Patent Application Laid-Open Publication No. Hei1-105738, for example).
- This photoreaction initiator may be selected from one or more type of benzoin derivatives, ketoneoxime derivatives, benzophenone derivatives and thioxanthone derivatives.
- ultraviolet curing polyol acrylate-based resin examples include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacyrylate and the like.
- These resins are normally used in combination with a known photosensitizer.
- the above photoreaction initiator may also be used as the photosensitizer.
- acetophenone benzophenone, hydroxybenzophenone, Michier's ketone, ⁇ -amyloxime ester, tetramethyluram monosulfide, thioxanthone and the like and the derivatives thereof.
- an epoxy acrylate-based photoinitiator is used, n-butylamine, triethylamine, tri-n-butylphosphixne or the like may be used as a sensitizer.
- the amount of the photoreaction initiator or photosensitizer which is used in the ultraviolet curing resin composition is 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the composition.
- additives such as matte agent, surfactant and antistat may be added as necessary.
- the application composition of the present invention which contains the adhesion improver, binder resin and other additives is applied with a suitable organic solvent.
- the employable organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol and tert-butanol, ketones such as methylethylketone, methylisobutylketone and acetone, esters such as ethyl acetate, methyl acetate, ethyl lactate, isopropyl acetate, amyl acetate and ethyl butyrate, glycolethers (propyleneglycol mono (C1-C4) alkylether (specifically, propyleneglycol monomethylethylether (PGME), propyleneglycol monoethylether, propyleneglycol mono-n-propylether, propyleneglycol monoisopropylether, propyleneglycol monobut
- the above application composition may be applied by doctor coating, extrusion coating, slide coating, roll coating, gravure coating, wire bar coating, reverse coating, curtain coating, extrusion coating or extrusion coating with a hopper described in U.S. Pat. No. 2,681,294 specification, to form a layer having a dry thickness of normally 0.1 to 10 ⁇ m.
- the dry thickness is more preferably 0.1 to 5 ⁇ m, and particularly 0.1 to 3 ⁇ m.
- heating temperature is preferably 50° C. to 300° C., preferably 60° C. to 250° C., and more preferably 80° C. to 150° C. Although depending on the heating temperature, heating time is appropriately in a range of 3 to 300 minutes.
- the application composition containing the ultraviolet curing resin is irradiated with ultraviolet ray from a light source.
- a light source for example, a low-pressure mercury lamp, middle-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, carbon arc lamp, metalhalide lamp or xenon lamp may be used.
- irradiation conditions depend on the lamp, a sufficient irradiation dose is about 20 to 10,000 mJ/cm 2 , and preferably 50 to 2,000 mJ/cm ⁇ 1 .
- a sensitizer having an absorption maximum within such range may be used.
- the base film of the present invention where the adhesion improver containing resin layer of the present invention is provided is preferably a polymer film, but not particularly limited.
- the base film is preferably to be easily produced, optically uniform and optically transparent.
- the base film may be any film such as cellulose acylate-based film, polyester-based film, polycarbonate-based film, polyarylate-based film, polysulfone (including polyethersulfone)-based film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylenevinyl alcohol film, syndiotactic polystyrene-based film, polycarbonate film, norbornene resin-based film, polymethylpentene film, polyether ketone film, polyether ketone imide film, polyamide film,
- These films are preferably manufactured by solution film casting or melt casting.
- cellulose acylate film, polycarbonate film, polysulfone (including polyethersulfone), cycloolefin resin film are preferable.
- cellulose acylate film and cycloolefin resin film are particularly preferable in terms of manufacturing, cost, transparency, uniformity, adhesiveness and the like.
- the followings are descriptions of the cellulose acylate and cycloolefin resin of the cellulose acylate film and cycloolefin resin film which are preferable for the present invention.
- the base film of the present invention where the adhesion improver containing resin layer of the present invention is provided contains cellulose acylate used for an optical film.
- Such a cellulose acylate preferably has an aliphatic acyl group having two or more carbon atoms, and more preferably has a total acyl substitution degree of 1.0 to 2.95 and a total acyl carbon number of 2.0 to 9.5.
- the total acyl carbon number of the cellulose acylate is preferably 4.0 to 9.0, and more preferably 5.0 to 8.5.
- the total acyl carbon number represents the sum of products of the substitution degree and the carbon number of respective acyl groups on a glucose unit of the cellulose acylate.
- the carbon number of the aliphatic acyl group is preferably from two or more to six or less, more preferably from two or more to four or less in terms of productivity and cost of cellulose synthesis.
- the portions not substituted with acyl groups normally exists in the form of hydroxyl groups.
- the glucose units which constitute cellulose with ⁇ -1,4-glycoside bond have free hydroxy (hydroxyl) groups at 2-, 3- and 6-positions.
- the cellulose acylate of the present invention is a polymer where such hydroxy (hydroxyl) groups are partially or fully esterified by acyl groups.
- the acyl substitution degree represents the sum of the esterification proportions of cellulose at 2-, 3- and 6-positions of the repeating unit. Specifically, the substitution degree is one when the hydroxy (hydroxyl) groups at each of 2-, 3- and 6-positions of cellulose are esterified by 100%. Thus, if cellulose is esterified at all 2-, 3- and 6-positions by 100%, the substitution degree is the maximum value, namely three.
- acyl group examples include, for example, acetyl group, propionyl group, butyryl group, pentanate group, hexanate group and the like
- the cellulose acylate may be a mixed aliphatic acid ester such as cellulose acetate, cellulose acetate-propionate, cellulose propionate, cellulose acetate-butyrate or cellulose aceate-pentanate, as long as the above side chain carbon number is satisfied.
- these cellulose acetates triacetyl cellulose, diacetyl cellulose and the like are preferable for an optical film.
- a preferable cellulose acylate has acyl substituents of 2 to 4 carbon atoms which fulfills both of the following inequalities (I) and (II) where X represents the acetyl substitution degree, and Y represents the propionyl or butyryl substitution degree.
- I inequalities
- II the acetyl substitution degree
- Y the propionyl or butyryl substitution degree.
- the portions not substituted with an acyl group normally exists in the form of a hydroxy (hydroxyl) group.
- the acyl substitution degree can be measured according to ASTM-D817-96.
- the cellulose acylate of the present invention has a weight average molecular weight Mw of preferably 50,000 to 500,000, more preferably 100,000 to 300,000, and further more preferably 150,000 to 250,000.
- the average molecular weight and molecular weight distribution of the cellulose acylate can be measured by high-performance liquid chromatography. Accordingly, the weight average molecular weight (Mw) and molecular weight distribution are calculated using the above technique.
- the measurement conditions are as follows.
- Cellulose the raw material of the acylate cellulose of the present invention, may be wood pulp or cotton linter.
- the wood pulp may be of either softwood or hardwood, but softwood pulp is preferably used.
- the cellulose acylate made from these sources of cellulose may be used alone or as a suitable mixture.
- the ratio of cellulose acylate made from cotton linter:cellulose acylate made from wood pulp (softwood):cellulose acylate made from wood pulp (hardwood) may be 100:0:0, 90:10:0, 85:15:0, 50:50:0, 20:80:0, 10:90:0, 0:100:0, 0:0:100, 80:10:10, 85:0:15 or 40:30:30.
- the cellulose preferably has a high polymerization degree.
- the cellulose is preferably linter pulp.
- the cellulose to be used is preferably composed of at least linter pulp.
- the ⁇ -cellulose content as an indication of cellulose crystallinity is 90% or more (for example, about 92 to 100%, preferably 95 to 100%, and more preferably 99.5 to 100% or around).
- the cellulose acylate of the present invention may be produced by a known method.
- cellulose as the raw material is mixed with a predetermined organic acid (acetic acid, propionic acid or the like), acid anhydride (acetic anhydride, propionic anhydride or the like) and a catalyst (sulfuric acid or the like) so as to esterify the cellulose, and the reaction is continued until cellulose triester is formed.
- a catalyst sulfuric acid or the like
- the cellulose triester is hydrolyzed to synthesize cellulose acylate having a desired acyl substitution degree. Thereafter, filtration, precipitation, washing with water, dehydration, drying and the like are performed, and then the cellulose acylate is obtained.
- the cycloolefin resin which is suitable for the component of the base film of the present invention is a non-crystalline resin having alicyclic structure(s) in the main and/or side chain.
- the alicyclic structure of the cycloolefin resin may be saturated alicyclic hydrocarbon (cycloalkane) structure, unsaturated alicyclic hydrocarbon (cycloalkene) structure or the like. In terms of mechanical strength, heat resistance and the like, cycloalkane structure is preferable.
- the number of carbon atoms constituting the alicyclic structure is not particularly limited. However, it is advantageous that the characteristics of mechanical strength, heat resistance and film moldability are highly balanced when the number of carbon atoms is 4 to 30 in general, preferably 5 to 20, and more preferably 5 to 15.
- the proportion of the repeating unit including the alicyclic structure and constituting the cycloolefin resin is preferably 55 mass % or more, more preferably 70 or more mass %, particularly 90 mass % or more. In terms of transparency and heat resistance, it is preferable that the proportion of the repeating unit including the alicyclic structure in the cycloolefin resin is within these ranges.
- cycloolefin resin examples include norbornene-based resin, monocyclic olefin-based resin, cyclic conjugated diene-based resin, vinyl alicyclic hydrocarbon-based resin, and hydrogenated products of these resins.
- norbornene-based resin is suitably used because of its good transparency and moldability.
- Examples of the norbornene-based resin include, for example, ring-opening polymers of monomers having a norbornene structure, ring-opening copolymers of monomers having a norbornene structure and other monomers, and the hydrides of the polymers or copolymers; addition polymers of monomers having a norbornene structure, addition copolymers of monomers having a norbornene structure and other monomers, the hydrides of the polymers or copolymers and the like.
- the hydrides of the open-ring (co)polymer of monomers having a norbornene structure is particularly suitable in terms of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, light-weight and the like.
- Examples of the monomers having a norbornene structure include bicylco[2.2.1]hept-2-ene (trivial name: norbornene), tricyclo[4.30.12,5]deca-3,7-diene (trivial name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.2, 5]deca-3-ene (trivial name: methanotetrahydrofluorene), tetracyclo[4.4.0.2,5.17,10]dodeca-3-ene (trivial name: tetracyclododecene) and derivatives of these compounds (e.g., a derivative having substituent(s) at the ring).
- substituents examples include, for example, an alkyl group, alkylene group and polar group and the like.
- a plurality of substituents, which may be the same or different, may be bonded to the ring.
- the monomers having a norbornene structure may be used alone, or two or more types of which can be combined.
- Types of polar group include hetero atoms, atomic groups having hetero atoms and the like.
- the hetero atoms include an oxygen atom, nitrogen atom, sulfur atom, silicon atom, halogen atom and the like.
- Specific examples of the polar groups include carboxy group, carbonylaoxycarbonyl group, epoxy groups, hydroxy group, oxy groups, ester groups, silanol groups, silyl groups, amino group, nitrile group, sulfone groups and the like. In order to obtain a film having low saturated water absorption ratio, a lower amount of the polar groups is preferable, and absence of the polar groups is more preferable.
- Examples of other monomers which are polymerizable with the monomers having a norbornene structure by ring-opening copolymerization include monocyclicolefins such as cyclohexene, cycloheptene and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene and derivatives thereof; and the like.
- the ring-opening polymers of the monomers having a norbornene structure and the ring-opening copolymers of the monomers having a norbornene structure and other monomers copolymerizable therewith may be obtained by (co)polymerizing the monomers under the presence of a known ring-opening polymerization catalyst.
- Examples of other monomers which are polymerizable with the monomers having a norbornene structure by addition copolymerization include, for example, ethylene, propylene, ⁇ -olefins of 2 to 20 carbon atoms such as 1-butene and derivatives thereof; resins of cycloolefin such as cyclobutene, cyclopentene and cyclohexene and derivatives thereof; unconjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene; and the like. These monomers may be used alone or in combination of two or more of them. Among the above monomers, ⁇ -olefins are preferable, and ethylene is more preferable.
- the addition polymers of the monomers having a norbornene structure and the addition copoly ers of the monomers having a norbornene structure and other monomers copolymerizable therewith can be obtained by polymerizing the monomers under the presence of a known addition polymerization catalyst.
- the hydrides of the ring-opening polymers of the monomers having a norbornene structure, hydrides of the ring-opening copolymers of the monomers having a norbornene structure and other monomers copolymerizable therewith, hydrides of the addition polymers of the monomers having a norbornene structure and hydrides of the addition copolymers of the monomers having a norbornene structure and other monomers copolymerizable therewith may be obtained by such a way that a known hydrogenation catalyst containing a transition metal such as palladium is added to a solution of a ring-opening (co)polymer or addition (co)polymer, and the solution is then made contact with hydrogen so that carbon-carbon unsaturated bonds are hydrogenated preferably by 90% or more.
- preferable resins have repeating units of X: bicyclo[3.3.0]octane-2,4-diyl-ethylene structure and Y: tricyclo[4.3.0.12,5]decane-7,9-diyl-ethylene structure, wherein the content of these repeating units are 90% or more with respect to all repeating units of the norbornene-based resin, and the ratio of X content to Y content, X:Y, is 100:0 to 40:60 by mass.
- the molecular weight of the cycloolefin resin which is suitably used in the present invention is appropriately selected according to the purpose of use.
- the weight average molecular weight (Mw) is normally 15,000 to 50,000, preferably 18,000 to 45,000, more preferably 20,000 to 40,000 in polyisoprene equivalent (polystyrene equivalent if the solvent is toluene), which is measured by gel permeation chromatography using cyclohexane (toluene if the resin is insoluble) as a solvent. If the weight average molecular weight is within these ranges, it is advantageous that the mechanical strength and moldability of the film are highly balanced.
- the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the cycloolefin resin which is suitably used in the present invention is in a range of normally 1.0 to 10.0, preferably 1.1 to 4.0, and more preferably 1.2 to 3.5, but not particularly limited.
- Glass transition temperature of the cycloolefin resin which is used in the present invention may be appropriately selected according to the purpose of use, and is in a range of preferably 80° C. or more, and more preferably 100 to 250° C. Films composed of a thermoplastic resin having a glass transition temperature within these ranges is excellent in durability, without causing deformation or stress under high temperature.
- the base film of the present invention contains a plasticizer, retardation adjuster, anti-deterioration agent (antioxidant), stripping aid, surfactant, dye, fine particles and the like.
- plasticizers may be used in the base film.
- the plasticizer is selected from polycarboxylate-based plasticizers, glycolate-based plasticizers, phthalate-based plasticizers, aliphatic acid ester-based plasticizers, polyol ester-based plasticizers, ester-based plasticizers, acrylic plasticizers and the like.
- plasticizers When two or more types of plasticizers are used, it is preferable that at least one type is a polyol ester-based plasticizer.
- the polyol ester-based plasticizer is a plasticizer composed of an ester of an aliphatic polyol containing two or more hydroxyl groups and a monocarboxylic acid, and preferably have an aromatic ring or cycloalkyl ring in the molecule. Aliphatic polyol-based esters containing 2 to 20 hydroxyl groups are preferable.
- polyols which are preferably used in the present invention are represented by the following general formula (a).
- R 11 represents an n-valent organic groups, n in the formula is a positive integer of 2 or more and the OH group represents an alcoholic and/or phenolic hydroxy (hydroxyl) group.
- Examples include adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like.
- triethylene glycol triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropyleneglycol, sorbitol, trimethylolpropane and xylitol are preferable.
- the monocarboxylic acids used for the polyol esters are not particularly limited, and may be a known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like. It is preferable to use an alicyclic monocarboxylic acid or aromatic monocarboxylic acid because moisture permeability and retainability are improved.
- Preferable aliphatic monocarboxylic acids are linear or branched aliphatic acids having 1 to 32 carbon atoms.
- the carbon number is more preferably 1 to 20, particularly 1 to 10. It is preferable to contain acetic acid because miscibility with the cellulose acylate is increased. It is also preferable to mix acetic acid with other monocarboxylic acids.
- Preferable aliphatic monocarboxylic acids include saturated aliphatic acids such as acetic acid, propionic acid, butylic acid, valeric acid, carpoic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanonic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanoic acid, melissic acid and lacceric acid, unsaturated aliphatic acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid, and the like.
- Preferable aliphatic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
- aromatic monocarboxylic acids include benzoic acid, compounds having one to three alkoxylic group(s) such as alkyl, methoxy and ethoxy group at the benzene ring of benzoic acid, e.g., toluic acid, aromatic monocarboxylic acids having two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid and tetralin carboxylic acid, and derivatives of the above.
- benzoic acid is preferable.
- the molecular weight of the polyol esters is not particularly limited, but preferably 300 to 1,500, and more preferably 350 to 750. Larger molecular weight is preferable in terms of low volatility, while smaller molecular weight is preferable in terms of moisture permeability and miscibility with the cellulose acylate.
- the carboxylic acid one type, or a mixture of two or more types thereof can be used for the polyol ester.
- the OH groups in the polyols may be fully esterified or partially left as OH groups.
- glycolate-based plasticizers are alkylphthalyl alkyl glycolates.
- alkylphthalyl alkyl glycolates include, for example, methylphthalyl methyl glycolate, ethylphthalyl ethyl glycolate, propylphthalyl propyl glycolate, butylphthaly butyl glycolate, octylphthalyl octyl glycolate, methylphthalyl ethyl glycolate, ethylphthalyl methyl glycolate, ethylphthalyl propyl glycolate, methylphthalyl butyl glycolate, ethylphthalyl butyl glycolate, butylphthalyl methyl glycolate, butylphthalyl ethyl glycolate, propylphthalyl butyl glycolate, butylphthalyl propyl glycolate, methylphthalyl octyl glycolate, ethylphthalyl octyl glycolate, octylphthalyl methyl glycolate, octylphthalylphthaly
- phthalate-based plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dicyclohexyl terephthalate and the like.
- citrate-based plasticizers examples include acetyltrimethyl citrate, acetyltriethyl citrate, acetyltributyl citrate and the like.
- aliphatic acid ester-based plasticizers examples include butyl oleate, methylacetyl ricinolate, dibutyl sebacate and the like.
- phosphate-based plasticizers examples include triphenylphosphate, tricresylphosphate, cresyldiphenylphosphate, octyldiphenylphosphate, diphenylbiphenylphosphate, trioctylphosphate, tributylphosphate and the like.
- the polycarboxylate compounds are composed of an ester of an alcohol and polycarboxylic acid containing 2 or more carboxylic groups, and preferably 2 to 20 carboxylic groups. It is preferable that the aliphatic polycarboxylic acid has 2 to 20 carboxylic groups, and the aromatic polycarboxylic acid and alicyclic polycarboxylic acid have 3 to 20 carboxylic groups.
- the polycarboxylic acid is represented by the following general formula (b) R 12 (COOH) m1 (OH) n1 General formula (b)
- R 12 represents (m1+n1)-valent organic groups, m1 represents a positive integer of 2 or more, n1 is an integer of 0 or more, the COOH group represents a carboxylic group, and the OH group represents an alcoholic or phenolic hydroxy (hydroxyl) group.
- aromatic polycarboxylic acids having 3 or more carboxylic groups such as trimellitic acid, trimesic acid and pyromellitic acid, and derivatives thereof, aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid and tetrahydrophthalic acid, oxy polycarboxylic acids such as tartaric acid, tartronic acid, malic acid and citric acid, and the like.
- oxypolycarboxylic acids are preferably used in terms of improvement in retainability.
- the alcohol of the polycarboxylate compound which may be used in the present invention is not particularly limited, and may be known alcohols or phenols.
- saturated or unsaturated linear or branched aliphatic alcohols having 1 to 32 carbon atoms are preferably used.
- the carbon number is more preferably 1 to 20, particularly 1 to 10.
- alicyclic alcohols such as cyclopentanol and cyclohexanol and derivatives thereof, aromatic alcohols such as benzylalcohol and cinnamylalcohol and derivatives thereof, and the like may be preferably used.
- Particularly preferable polycarboxylate compounds include, for example, triethyl citrate, tributyl citrate, acetyltriethyl citrate (ATEC), acetyltributyl citrate (ATBC), benzoyltributyl citrate, acetyltriphenyl citrate, acetyltribenzyl citrate, dibutyl tartarate, diacetyldibutyl tartarate, tributyl trimellitate, tetrabutyl pyromellitate and the like.
- TAC acetyltriethyl citrate
- ATBC acetyltributyl citrate
- benzoyltributyl citrate acetyltriphenyl citrate
- acetyltribenzyl citrate dibutyl tartarate
- diacetyldibutyl tartarate diacetyldibutyl tartarate
- phase difference reducer anti-deteriorating agent, stripping agent, matte agent, lubricant and the like may be appropriately used as necessary.
- the base film of the present invention preferably has no phase difference, it is preferable to use a polymer which can reduce phase difference.
- the polymer has a repeating unit in the compound, and preferably has a number average molecular weight of 700 to 10,000.
- the number average molecular weight is more preferably 700 to 8,000, further more preferably 700 to 5,000, particularly 1,000 to 5,000.
- the polymer is selected from polyester-based polymer, styrene-based polymer, acrylic polymer and copolymers thereof, and is preferably aliphatic polyester, acrylic polymer or styrene-based polymer. It is preferable that at least one polymer having negative intrinsic birefringence such as styrene-based polymer and acrylic polymer is contained.
- the polyester-based polymer is a polymer which is obtained by the reaction of an aliphatic dicarboxylic acid having 2 to 20 carbon atoms with at least one diol compound selected from aliphatic diols having 2 to 12 carbon atoms and alkylether diols having 4 to 20 carbon atoms, where both ends of the reaction product may be left unchanged, or may be reacted with a monocarboxylic acid, monoalcohol or phenol, i.e., so-called end-capped. This end-capping is performed particularly in order to exclude free carboxylic acids, and thus effective in terms of storage stability and the like.
- the dicarboxylic acid which is used for the polyester-based polymer of the present invention is an aliphatic dicarboxylic acid residue having 4 to 20 carbon atoms or aromatic dicarboxylic acid residue having 8 to 20 carbon atoms.
- Examples of the aliphatic dicarboxylic acid having 2 to 20 carbon atoms which is preferably used in the present invention include, for example, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane dicaroxylic acid and 1,4-cyclohexane dicarboxylic acid.
- preferable aliphatic dicarboxylic acids are malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid and 1,4-cyclohexane dicarboxylic acid.
- Particularly preferable aliphatic dicarboxylic acids are succinic acid, glutaric acid, and adipic acid.
- the diol used for the polymer is, for example, selected from aliphatic diols having 2 to 20 carbon atoms and alkyletherdiols having 4 to 20 carbon atoms.
- Examples of the aliphatic diols having 2 to 20 carbon atoms include alkyldiols and alicyclic diols such as ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentylglycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1
- Preferable aliphatic diols are ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol and 1,4-cyclohexane dimethanol.
- ethanediol 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol and 1,4-cyclohexane dimethanol are preferable.
- alkyletherdiols having 4 to 20 carbon atoms preferably include, for example, polytetramethylene etherglycol, polyethylene etherglycol and polypropylene etherglycol, and combinations thereof.
- the average degree of polymerization is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly 2 to 4.
- Examples of the above include Carbowax resin, Pluronics resin and Niax resin as typically useful commercially available polyetherglycols.
- the polymer is end-capped with an alkyl group or aromatic group.
- Protecting the ends with hydrophobic functional groups is effective against aging degradation under hot and humid condition because the protection delays hydrolysis of the ester groups.
- both ends of the polyester additive which is used in the present invention are protected with monoalcohol residues or monocarboxylic acid residues so that carboxylic acids or OH groups are not left at the ends.
- the monoalcohol is preferably a substituted or unsubstituted monoalcohol having 1 to 30 carbon atoms, examples of which include aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanolnol, isopentanol, hexanol, isohexanol, cyclohexylalcohol, octanol, isooctanol, 2-ethylhexylalcohol, nonylalcohol, isononylalcohol, tert-nonylalcohol, decanol, doadecanol, dodecahexanol, dodecaoctanol, allylalcohol and oleylalcohol, substituted alcohols such as benzylalcohol and 3-phenylpropanol, and the like.
- Preferably used end-capping alcohols are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, isopentanol, hexanol, isohexanol, cyclohexylalcohol, isooctanol, 2-ethylhexylalcohol, isononylalcohol, oleylalcohol and benzylalcohol, of which methanol, ethanol, propanol, isobutanol, cyclohexylalcohol, 2-ethylhexylalcohol, isononylalcohol and benzylalcohol are particularly preferred.
- the monocarboxylic acid used for the monocarboxylic residues is preferably a substituted or unsubstituted monocarboxylic acid having 1 to 30 carbon atoms.
- the above may also be an aliphatic monocarboxylic acid or aromatic ring-containing carboxylic acid.
- Preferable aliphatic monocarboxylic acids include acetic acid, propionic acid, butane acid, caprylic acid, carpoic acid, decane acid, dodecane acid, stearic acid and oleic acid.
- aromatic monocarboxylic acids include, for example, benzoic acid, p-tert-butylbenzoic acid, p-tert-amylbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, aminobenzoic acid, acetoxybenzoic acid and the like.
- the above monocarboxylic acids may be each used alone, or two or more of the above monocarboxylic acids may be used in combination.
- the polymer used in the present invention can be easily synthesized by an ordinary method of either thermal melt condensation by polyesterification or transesterification of the above dicarboxylic acid and diol and/or end-capping monocarboxylic acid or monoalcohol, or interfacial condensation of acid chlorides of these acids and glycols.
- polyester-based additives can be found in “Additives—theory and application—” by Koichi Murai (Sawai Shobo, Co., issued on Mar. 1, 1973 (first edition, first print)).
- materials described in Japanese Patent Application Laid-Open Publications Nos. Hei5-155809, Hei5-155810, Hei5-197073, 2006-259494, Hei7-330670, 2006-342227, 2007-003679 and the like may also be used.
- the styrene-based polymers preferably have a structural unit represented by the general formula (1) which is derived from an aromatic vinyl monomer.
- R 101 to R 104 each independently represent a polar group or substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atom(s) which may have a linking group having hydrogen atom(s), halogen atom(s), oxygen atom(s), sulfur atom(s), nitrogen atom(s) or silicon atom(s); and R 104 may be the same or different atom or group, and may bond together to form a carbon ring or hetero ring (these carbon ring and hetero ring may have monocyciic structure or polycyclic structure by condensation with another ring).
- aromatic vinyl monomer examples include styrene; alkyl substituted styrenes such as ⁇ -methylstyrene, ⁇ -methylstyrene and p-methylstyrene; halogen substituted styreres such as 4-chlorostyrene and 4-bromostyrene; hydroxystyrenes such as p-hydroxystyrene, ⁇ -methyl-p-hydroxystyrene, 2-methyl-4-hydroxystyrene and 3,4-dihydroxystyrene; vinylbenzylalcohols; alkoxy substituted styreres such as p-methoxystyrene, p-tert-butoxystyrene and m-tert-butoxystyrene; vinyl benzoic acids such as 3-vinylbenzoic acid and 4-vinylbenzoic acid; vinyl benzoates such as methyl-4-vinylbenzoate and ethyl-4
- the above acrylic polymers have a structural unit derived from an acrylate-based monomer which is represented by the general formula (2)
- R 105 to R 108 each independently represent a polar group or substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atom(s) which may have a linking group with hydrogen atom(s), halogen atom(s), oxygen atom(s), sulfur atom(s), nitrogen atom(s) or silicon atom(s).
- acrylate-based monomer examples include, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, tert-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), mysrityl acrylate (n-, i-), (2-ethylhexyl)acrylate, ( ⁇ -caprolactone)acrylate, (2-hydroxyethyl)acrylate, (2-hydroxypropyl)acrylate, (3-hydroxypropyl)acrylate, (4-hydroxybutyl)acrylate, (2-hydroxybutyl)acrylate, (2-methoxyethyl)acrylate, (2-
- Two or more of these monomers may be used in combination as copolymer components.
- these monomers methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, tert-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-) and corresponding methacrylates of these acrylates are preferred because of their good industrial availability and low cost.
- the above copolymer includes at least one structural unit derived from the aromatic vinyl monomer represented by the general formula (1) or the acrylate-based monomer represented by the general formula (2).
- R 101 to R 104 each independently represents a polar group or substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atom(s) which may have a linking group with a hydrogen atom, halogen atom, oxygen atom, sulfur atom, nitrogen atom or silicon atom; R 104 may be the same or different atom or group, and may bond together to form a carbon ring or hetero ring (these carbon ring and hetero ring may have monocyclic structure or form polycyclic structure by condensation with another ring).
- R 105 to R 108 each independently represent a polar group or substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atom(s) which may have a linking group with a hydrogen atom, halogen atom, oxygen atom, sulfur atom, nitrogen atom or silicon atom. Further, it is preferable that the structure other than the above monomers which constitutes a copolymer composition has good copolymerizability with the above monomers.
- Examples of such structures include acid anhydrides such as maleic anhydride, citraconic anhydride, cis-1-cyclohexene-1,2-dicarboxylic anhydride, 3-methyl-cis-1-cyclohexene-1,2-dicarboxylic anhydride and 4-methyl-cis-1-cyclohexene-1,2-dicarboxylic anhydride; nitrile group-containing radical polymerizable monomers such as acrylonitrile and methacrylonitrile; amide bond-containing radical polymerizable monomers such as acrylicamide, methacrylicamide and trifluoromethane sulfonylaminoethyl (meth)acrylate; aliphatic acid vinyls such as vinyl acetate; chlorine containing radical polymerizable monomers such as vinyl chloride and vinylidene chloride; conjugated diolefins such as 1,3-butadiene, isoprene and 1,4-dimethylbutadiene, but the present invention is not limited
- the low-molecular-weight additive may be solid or oily matter. That is, the low-molecular-weight additive is not particularly limited by its melting point and boiling point.
- an ultraviolet absorbing material having a melting point of 20° C. or more and an ultraviolet absorbing material having a melting point of 20° C. or less may be mixed, and similarly, anti-deterioration agents may be mixed.
- infrared absorbing materials are described in, for example, Japanese Patent Application Laid-Open Publication No. 2001-194522.
- Adding the low-molecular-weight additive may be performed at any timing in a cellulose acylate solution (dope) production, or a step of adding the additive may be performed in the last preparation step of a dope preparation process. Further, the amount of each material to be added is not particularly limited as long as it can exert the advantages.
- the low-molecular-weight additive may be any compound represented by the following formulae (3) to (7)
- R 1 represents an alkyl group or aryl group
- R 2 and R 3 each independently represent a hydrogen atom, alkyl group or aryl group.
- the total carbon number of R 1 , R 2 and R 3 is 10 or more
- R 4 and R 5 each independently represent an alkyl group or aryl group.
- the total carbon number of R 4 and R 5 is 10 or more.
- R 1 represents an alkyl group or aryl group
- R 2 and R 3 each independently represent a hydrogen atom, alkyl group or aryl group. It is particularly preferable that the total carbon number of R 1 , R 2 and R 3 are 10 or more.
- R 4 and R 5 each independently represent an alkyl group or aryl group. The total carbon number of R 4 and R 5 is 10 or more, and each alkyl or aryl group may have a substituent.
- substituents include a fluorine atom, alkyl group, aryl group, alkoxy group, sulfone group and sulfoneamide group.
- alkyl group aryl group, alkoxy group, sulfone group and sulfoneamide group are preferable.
- the alkyl group may be a linear, branched or cyclic group having preferably 1 to 25 carbon atom(s), more preferably 6 to 25 carbon atoms, and particularly 6 to carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, bicyclooctyl group, nonyl group, adamantyl group, decyl group, tert-octyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl
- the alkyl group preferably has 6 to 30 carbon atoms, and particularly 6 to 24 carbon atoms (e.g., phenyl group, biphenyl group, terphenyl group, naphthyl group, binaphthyl group and triphenylphenyl group).
- 6 to 24 carbon atoms e.g., phenyl group, biphenyl group, terphenyl group, naphthyl group, binaphthyl group and triphenylphenyl group.
- the followings are preferable examples of the compounds represented by the general formulae (3) and (4), but the present invention is not limited to these specific examples.
- the compounds represented by the general formula (3) may be obtained by condensation reaction of a sulfonylchloride derivative with an amine derivative.
- the compounds represented by the general formula (4) may be compounds represented by the general formula (4) may be obtained by oxidation reaction of a sulfide or Friedel-Crafts reaction of a sulfonic acid chloride with an aromatic compound.
- R 11 represents an aryl group.
- R 12 and R 13 each independently represent an alkyl or aryl group where at least one of R 12 and R 13 is an aryl group. If R 12 is an aryl group, R 13 may be an alkyl group or aryl group, but an alkyl group is more preferable.
- the alkyl group may be a linear, branched or cyclic group having preferably 1 to 20 carbon atom(s), more preferably 1 to 15 carbon atom(s), and most preferably 1 to 12 carbon atom(s).
- the aryl group preferably has 6 to 36 carbon atoms, and more preferably 6 to 24.
- R 21 , R 22 and R 23 each independently represent an alkyl group.
- the alkyl group may be linear, branched or cyclic.
- R 21 is preferably a cyclic alkyl group, and it is more preferable that at least one of R 22 and R 23 is a cyclic alkyl group.
- the alkyl group preferably has 1 to 20 carbon atom(s), more preferably 1 to carbon atom(s), and most preferably 1 to 12 carbon atom(s).
- the cyclic alkyl group is preferably a cyclohexyl group.
- the alkyl and aryl groups of the above general formulae (5) and (6) may each have a substituent.
- substituents include a halogen atom (e.g. chlorine, bromine, fluorine and iodine), alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, sulfonylamino group, hydroxy group, cyano group, amino group and acylamino group, of which a halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, sulfonylamino group and acylamino group are more preferable.
- an alkyl group, aryl group, sulfonylamino group and acylamino group are preferable.
- R 31 , R 32 , R 33 and R 44 each represent a hydrogen atom, substituted or unsubstituted aliphatic group, or substituted or unsubstituted aromatic group, of which an aliphatic group is preferable.
- the aliphatic group may be linear, branched or cyclic, and more preferably cyclic. Possible substituents of the aliphatic and aromatic groups include the substituent T described below, but the aliphatic and aromatic groups are preferably unsubstituted.
- X 31 , X 32 , X 33 and X 34 each represent a divalent linking group composed of at least one group selected from a single bond, —CO—, NR 35 — (R 35 represents a substituted or unsubstituted aliphatic group, or substituted or unsubstituted aromatic group, of which substituted groups and/or an aliphatic group are more preferable).
- R 35 represents a substituted or unsubstituted aliphatic group, or substituted or unsubstituted aromatic group, of which substituted groups and/or an aliphatic group are more preferable.
- combinations of X 31 , X 32 , X 33 and X 34 are preferably selected from —CO— and —NR 35 —.
- a, b, c and d are each an integer of 0 or more, preferably 0 or 1 where a+b+c+d is 2 or more, preferably 2 to 8, more preferably 2 to 6, and further more preferably 2 to 4.
- Z 31 represents an organic group (excluding cyclic groups) having a valence of (a+b+c+d).
- the valence number of Z 31 is preferably 2 to 8, more preferably 2 to 6, further preferably 2 to 4, and most preferably 2 or 3.
- the organic group represents a group composed of an organic compound.
- R 311 and R 312 each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, of which an aliphatic group is preferable.
- the aliphatic group may be linear, branched or cyclic, and preferably cyclic.
- Possible substituents of the aliphatic and aromatic groups include the substituent T described below, but the aliphatic and aromatic groups are preferably unsubstituted.
- X 311 and X 312 each independently represent —CONR 313 — or NR 314 CO—, where R 313 and R 314 represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, of which unsubstituted groups and/or an aliphatic group are more preferable.
- Z 311 represents a divalent organic group (excluding cyclic groups) composed of at least one group selected from —O—, —S—, —SO—, —SO 2 —, —CO—, —NR 315 — (R 315 represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, of which unsubstituted groups and/or an aliphatic group are more preferable), alkylene group and arylene group.
- a combination of Z 311 is preferably selected from —O—, —S—, —NR 315 — and alkylene group, more preferably selected from —O—, —S— and alkylene group, and most preferably selected from —O—, —S— and alkylene group.
- R 321 , R 322 , R 323 and R 324 each represent a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, of which an aliphatic group is preferable.
- the aliphatic group may be linear, branched or cyclic, and preferably cyclic.
- Possible substituents of the aliphatic and aromatic groups include the substituent T described below, but the aliphatic and aromatic groups are preferably unsubstituted.
- Z 321 represents a divalent organic group (excluding cyclic groups) composed of at least one group selected from —O—, —S—, —SO—, —SO 2 —, —CO—, —NR 325 — (R 325 represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, of which unsubstituted groups and/or an aliphatic group are preferable), alkylene group and arylene group.
- a combination of Z 321 is preferably selected from —O—, —S—, —NR 325 — and alkylene group, more preferably selected from —O—, —S— and alkylene group, and most preferably selected from —O—, —S— and alkylene group.
- the above substituted or unsubstituted aliphatic groups will be described below.
- the aliphatic groups may be linear, branched or cyclic group having preferably 1 to carbon atom(s), more preferably 6 to 25 carbon atoms, and particularly 6 to 20 carbon atoms.
- aliphatic groups include, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, bicyclooctyl group, adamantyl group, n-decyl group, tert-octyl group, dodecyl group, hexadecyl group, octadecyl group, didecyl group and the like.
- the aromatic groups may be an aromatic hydrocarbon group or aromatic heterocyclic group, of which an aromatic hydrocarbon group is more preferable.
- the aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms.
- Specific examples of the ring of the aromatic hydrocarbon group include, for example, benzene, naphthalene, anthracene, biphenyl or terphenyl rings.
- Particularly preferable aromatic hydrocarbon groups are a benzene, naphthalene and biphenyl groups.
- the aromatic heterocyclic group preferably has at least one of oxygen, nitrogen and sulfur atoms.
- heterocycle examples include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthlazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaindene and the like.
- aromatic heterocyclic groups are pyridine, triazine and quinoline.
- substituent T examples include, for example, alkyl groups (alkyl groups having preferably 1 to 20 carbon atom(s), more preferably 1 to 12 carbon atom(s), particularly 1 to 8 carbon atom(s), e.g., a methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like), alkenyl groups (alkenyl groups having preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly 2 to 8 carbon atoms, e.g., a vinyl group, aryl group, 2-butenyl group, 3-pentenyl group and the like), alkynyl groups (alkynyl groups having preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atom
- sulfinyl groups sulfinyl groups having preferably 1 to 20 carbon atom(s), more preferably 1 to 16 carbon atom(s), particularly 1 to 12 carbon atom(s), e.g., a methane sulfinyl group, benzene sulfinyl group and the like
- ureide groups ureide groups having preferably 1 to carbon atom(s), more preferably 1 to 16 carbon atom(s), particularly 1 to 12 carbon atom(s), e.g., an ureido group, methylureido group, phenylureido group and the like
- phospholic amide groups phospholic amide groups having preferably 1 to 20 carbon atom(s), more preferably 1 to 16 carbon atom(s), particularly 1 to 12 carbon atom(s), e.g., a diethylphosphoramide, phenylphosphoramide and the like
- heterocylic groups heterocylic groups having preferably 1 to 30 carbon atom(s), more preferably 1 to 12 carbon atom(s), where the hetero atom is, for example, a nitrogen atom, oxygen atom or sulfur atom, e.g., an imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl groups (silyl groups having preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly 3 to 24 carbon atoms, e.g.,
- the compounds of the general formulae (5), 6) and (7) may be obtained by dehydration-condensation reaction of a carboxylic acid and amine using a condensation agent (e.g., dicyclohexylcarbodiimide (DCC) and the like) or by substitution reaction of a carboxylic acid chloride derivative with an amine derivative.
- a condensation agent e.g., dicyclohexylcarbodiimide (DCC) and the like
- DCC dicyclohexylcarbodiimide
- plasticizers of cellulose acylate may be usefully used as the retardation reducer of the present invention.
- Such plasticizers may be phosphates or carboxylates.
- the phosphates include triphenyl phosphate (TPP) and tricresylphosphate (TCP).
- TPP triphenyl phosphate
- TCP tricresylphosphate
- Representatives of the carboxylates are phthalates and citrates.
- the phthalates include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP).
- Examples of the cirticates include O-acetyltriethnyl citrate (OACTE) and O-acetyltributyl citrate (OACTB).
- Examples of other carboxylates include butyl oleate, methylacetyl ricinolate, dibutyl sebacate and various trimellitates.
- Phthalate-based plasticizers DMP, DEP, DEP, DOP, DPP and DEHP are preferably used. Particularly, DEP and DPP are preferred.
- the retardation reducer which is used in the present invention is a retardation reducer for thickness retardation (Rth).
- Rth reducers include aliphatic polyesters, acrylic polymers, styrene polymers and lower-molecular-weight compounds of the general formulae (3) to (7), of which aliphatic polyesters, acrylic polymers and styrene polymers are preferable, and aliphatic polyesters and acrylic polymers are more preferable.
- the retardation reducer is added in a proportion of 0.01 to 30 mass % with respect to the base film, more preferably in a proportion of 0.1 to 20 mass %, and particularly in a proportion of 0.1 to 10 mass %.
- the base film solution may be added with a known anti-deterioration (anti-oxidation) agent, for example, a phenolic or hydroquinone-based antioxidation agent such as 2,6-di-tert-butyl-4-methylphenol, 4,4′-thiobis-(6-tert-butyl-3-methylphenol), 1,1′-bis(4-hydroxyphenyl)cyclohexane, 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone or pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].
- a known anti-deterioration (anti-oxidation) agent for example, a phenolic or hydroquinone-based antioxidation agent such as 2,6-di-tert-butyl-4-methylphenol, 4,4′-thiobis-(6-ter
- a phosphorus antioxidant such as tris(4-methoxy-3,5-diphenyl)phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite or bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.
- the anti-deterioration agent is added in an amount of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the base resin.
- the base film of the present invention contains a stripping agent in order to further improve the stripping characteristics.
- the stripping agent may be contained, for example, in a proportion of 0.001 to 1 mass %.
- the stripping promoting agent is added in an amount of 0.5 mass % or less, it is advantageous that the stripping promoting agent is less separated from the film.
- it is added in an amount of 0.005 mass % or more it is advantageous that desired stripping reducing effect is obtained.
- the stripping promoting agent is thus contained preferably in a proportion of 0.005 to 0.5 mass %, and more preferably in a proportion of 0.01 to 0.3 mass %.
- stripping promoting agents are employable, such as organic or inorganic acid compounds, surfactants and chelating agents. Above all, polycarboxylic acids and esters thereof are effective. In particular, ethylesters of citric acid may be used effectively.
- fine particles are generally added to the base film especially in the present invention.
- Such fine particles are referred to as matte agents, blocking agents or anti-creak agents, and have been conventionally used.
- the fine particles are not particularly limited as long as having the above-described functions, and may be an inorganic or organic matte agent.
- the inorganic matte agent include silicon-containing inorganic compounds (e.g., silicon dioxide, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and the like), titanium oxide, zinc oxide, aluminum oxide, barium oxide, zirconium oxide, strontium oxide, antimony oxide, tin oxide, tin-antimony oxide, calcium carbonate, talc, clay, calcined kaolin, calcium phosphate and the like, of which silicon-containing inorganic compounds and zirconium oxide are more preferable, and silicon dioxide is particularly preferable because it can reduce the turbidity of the cellulose acylate film.
- silicon-containing inorganic compounds e.g., silicon dioxide, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and the like
- titanium oxide zinc oxide, aluminum oxide, barium oxide, zirconium oxide, strontium oxide, antimony oxide, tin oxide, tin-antimony oxide, calcium carbonate, talc, clay,
- the silicon dioxide fine particles may be a commercially available product, examples of which include, by the trade names, AEROSIL R972, R974, R812, 200, 300, R202, OX50 and TT600 (all by Nippon. Aerosil Co., Ltd.) and the like.
- the zirconium oxide fine particles may be a commercially available product, examples of which include, by the trade names, AEROSIL R976 and R811 (both by Nippon Aerosil Co., Ltd.) and the like.
- the organic compound matte agent include, for example, polymers such as silicone resins, fluororesins and acrylic resins, of which silicone resin is preferably used.
- silicone resins resins having three dimensional network are preferable.
- silicone resins include, by the trade names, TOSPEARL 103, TOSPEARL 105, TOSPEARL 108, TOSPEARL 120, TOSPEARL 145, TOSPEARL 3120 and TOSPEARL 240 (all by Toshiba Silicone Co.), for example.
- a method for adding matte agents to a base resin solution is not specifically limited, but may be any method as long as a desired base resin solution is obtained.
- the additive may be added in mixing the base resin with a solvent, or may be added after preparing the mixture solution of the base resin and the solvent. Further, the additive may be added and mixed just before casting the dope, which is so-called just-in-time addition, where a screw extruder is installed online for mixing.
- a static mixer such as an inline mixer is preferable.
- Preferable inline mixers include, for example, a static mixer SWJ (Toray static Inline mixer Hi-Mixer) (Toray Engineering Co., Ltd) and the like.
- Japanese Patent Application Laid-Open Publication No. 2003-053752 discloses a method for manufacturing a base film, wherein distance L between the tip of an addition nozzle and the front end of an inline mixer is not more than five times inner diameter d of a main material pipe, the addition nozzle mixing an additive of a different composition with main material dope, so that uneven concentration, aggregation of matte particles and the like are eliminated.
- the above publication also discloses that the distance (L) between the tip of the supply nozzle and the front end of the inline mixer is not more than 10 times inner diameter (d) of the tip opening of the supply nozzle, the supply nozzle supplying the additive of a different composition with the main material dope, and the inline mixer is a static non-agitating inline mixer or dynamic agitating inline mixer. More specifically, the above publication discloses that the flow volume ratio of the main material dope of the base resin film/the inline additive solution is 10/1 to 500/1, and preferably 50/1 to 200/1. Further, Japanese Patent Application Laid-Open Publication No.
- 2003-014933 which discloses an invention aiming to provide a phase difference film which has less bleed out of additives, no delamination between layers, and good slip characteristics and transparency, discloses such methods of adding an additive that an additive may be added in a melting furnace, or an additive or an additive solution or dispersion may be added to dope flowing between a melting furnace and a co-film casting die, and in the latter case, it is preferable to provide a mixing means such as a static mixer in order to improve mixing.
- the matte agent does not increase haze of the film unless it is added in a large amount, and thus cause less defects such as low contrast or bright points when it is actually used for an LCD. Further, unless the matte agent is added in a too little amount, creak and abrasion resistance can be achieved.
- the matte agent is contained in a proportion of preferably 0.01 to 5.0 mass %, more preferably 0.03 to 3.0 mass %, and particularly 0.05 to 1.0 mass %.
- the method for manufacturing the base film of the present invention will be described taking the cellulose acylate film as an example.
- the cellulose acylate film which is used in the present invention may be manufactured by either solution film casting or melt film casting, of which solution film casting is preferable.
- the manufacture of the cellulose acylate film which is used in the present invention is conducted according to the steps of dissolving the cellulose acylate and additives to solvent to prepare dope, casting the dope onto a metal support of a belt or drum shape, drying the casted dope to obtain a web, exfoliating the web from the metal support, stretching, further drying, as necessary further heat-treating the obtained film, and winding after cooling. It is preferable that the cellulose acylate film which is used in the present invention contains 60 to 95 mass % of the cellulose acylate on the solid content basis.
- cellulose acylate concentration in the dope is higher, because higher concentration can make the drying step after casting the dope onto the metal support easier.
- the concentration is preferably 10 to 35 mass %, and more preferably 15 to 25 mass %.
- the solvent which is used for the dope may be used alone or in a combination of two or more solvents. It is preferable to mix a good solvent and poor solvent of the cellulose acylate in terms of production efficiency, where the ratio of the good solvent is preferably higher in terms of solubility of the cellulose acylate.
- the mixing ratio of the good solvent to the poor solvent is preferably within a range of 70 to 98 mass % of the good solvent and 2 to 30 mass % of the poor solvent.
- the good solvent is defined as solvent which can dissolve the cellulose acylate by itself, and the poor solvent is defined as solvent which only swells the cellulose acylate or cannot dissolve the cellulose acylate.
- a solvent is the good or poor solvent depends on the acetyl substitution degree of the cellulose acylate. For example, when acetone is used as the solvent, it is the good solvent of cellulose acetate (acetyl substitution degree of 2.4), while acetone is the poor solvent of cellulose acetate (acetyl substitution degree of 2.8).
- examples of the good solvent which is used in the present invention include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, methylacetoacetate and the like. Particularly, methylene chloride and methyl acetate are preferred.
- preferable examples of the poor solvent which is used in the present invention include, for example, methanol, ethanol, n-butanol, cyclohexane and cyclohexanone and the like. It is preferable that the dope contains 0.01 to 2 mass % of water.
- the cellulose acylate may be dissolved by a general method. Combination of heating and pressurizing enables heating over a melting point under ordinary pressure. When the cellulose acylate is stirred and dissolved into solvent within such a temperature range that it is higher than the melting point of the solvent under ordinary pressure but the solvent does not boil under the pressure, it is advantageous that gel or undissolved clusters called “mamako” clumping) are prevented. Also preferably used is such a method that after the cellulose acylate is mixed with the poor solvent to be moist or swelled, the good solvent is then added to dissolve the cellulose acylate.
- the pressurizing may be performed by injecting inert gas such as nitrogen gas or by heating to increase vapor pressure of the solvent.
- the heating is preferably performed from outside.
- a jacket type heater is preferable because temperature control is easily performed.
- the heating temperature after adding the solvent is preferably higher, however excessively high heating temperature requires high pressure condition, which deteriorates the productivity.
- the heating temperature is preferably 45° C. to 120° C., more preferably 60° C. to 110° C., further preferably 70° C. to 105° C. Further the pressure is controlled so that the solvent does not boil at the set temperature.
- Cool dissolution is also preferably used, which enables dissolving the cellulose acylate into a solvent like methyl acetate.
- this cellulose acylate solution is filtrated with a suitable filter medium such as filter paper.
- a suitable filter medium such as filter paper.
- the filter medium has smaller absolute filter rating in terms of removing insoluble matter.
- the filter medium has an absolute filter rating preferably of 0.008 mm or less, more preferably 0.001 to 0,008 mm, and further preferably 0.003 to 0.006 mm.
- the material of the filter medium is not particularly limited, and an ordinary filter medium may be used.
- Plastic filter media made of polypropylene, TEFLON® or the like and metal filter media made of stainless steel or the like are preferred in terms of avoiding discharge of fiber or the like.
- the filtration is preferable for removing or reducing impurities, in particular bright-spot contaminants, included in the cellulose acylate as the raw material.
- the bright-spot contaminants are spots (contaminants) which gleam by light, when a cellulose acylate film is placed between two polarizing plates in crossed Nicol configuration, observed from the side of one polarizing plate under illumination from the side of the other polarizing plate.
- the number of bright spots having a size of 0.01 mm or more is 200 spots/cm 2 or less.
- Bright spots are more preferably 100 spots/cm 2 or less, further more preferably 50 spots/cm 2 or less, and further more preferably 0 to 10 spots/cm 2 or less. It is also preferable that there are less bright spots having a size of 0.01 mm or less.
- the dope may be filtered by an ordinary method, but it is preferable to perform the filtration with heat within such a temperature range that it is higher than a boiling point of the solvent under ordinary pressure but the solvent does not boil under the pressure, because difference in filter pressure before and after the filtration (called differential pressure) is small.
- the temperature is preferably 45° C. to 120° C., more preferably 45° C. to 70° C., and further more preferably is 45° C. to 55° C.
- filter pressure is lower.
- the filter pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further more preferably 1.0 MPa or less.
- the metal support used in the casting step has a mirror-finished surface.
- a stainless steel belt or a drum having a surface plated with cast metal is used.
- the cast width may be 1 to 4 m.
- surface temperature of the metal support is from ⁇ 50° C. to less than a melting point of the solvent. Higher temperature is preferable because the web can be dried faster, but excessively high temperature may cause blisters in the web or deterioration in flatness.
- Temperature of the support is preferably 0° C. to 55° C., and more preferably 25° C. to 50° C. Alternatively, it is also preferable that the support is cooled so that the web gels and then is stripped from the drum while the web contains a lot of residual solvent.
- the method of controlling the metal support temperature is not particularly limited, and may be a method of blowing hot or cold air or a method of contacting the back side of the metal support with hot water.
- the method using hot water is more preferable because heat transfer is efficient and the temperature thus becomes constant in a short time.
- the temperature of the hot air may be higher than a target temperature.
- a residual solvent amount is preferably 10 to 150 mass % at the time of stripping the web from the metal support, more preferably 20 to 40 mass % or 60 to 130 mass %, and particularly 20 to 30 mass % or 70 to 120 mass %.
- M represents the mass of a sample which is collected at a certain time like in the middle of production or after production
- N represents the mass of the sample M after dried at 115° C. for 1 hour.
- the web is further dried after stripped from the metal support so that the residual solvent amount is preferably 1 mass % or less, more preferably 0.1 mass % or less, particularly 0 to 0.01 mass % or less.
- the film drying step uses such a method that the web is dried while being conveyed by generally a roll drying method (the web is dried by alternately passing through a plurality of upper and lower rolls) or a tentering method.
- the web is stretched in the width (lateral) direction by a tentering method in which both ends of the web are pinched with clips or the like.
- the stretching method is not particularly limited.
- such methods include a method in which a plurality of rolls are controlled to have different circumferential velocities, and the web is stretched toward the longitudinal direction because of the difference in circumferential velocity between the rolls; a method in which both ends of the web is fixed with clips or pins and the gap between the ends is widen toward the traveling direction so that the web is stretched toward the longitudinal direction; a method in which the gap between both ends is widen in the same way toward the lateral direction so that the web is stretched toward the lateral direction; or a method in which the gap between the ends is widen toward both lateral and longitudinal directions simultaneously in the same way so that the web is stretched toward both lateral and longitudinal directions. Needless to say, these methods may be combined.
- the stretching may be performed toward the lateral direction, longitudinal direction or both directions with respect to the film forming direction.
- the stretching may be performed simultaneously or successively.
- tentering method it is preferable that the clips are driven by a linear drive system because it enables smooth stretching to reduce risk of fracture or the like.
- a stretching ratio in the stretching step is preferably 1.3 to 3.0, and more preferably 1.5 to 2.8. When the stretching ratio is within this range, it is advantageous that uneven thickness in the width direction is reduced. If stretching temperature is differentiated along the width direction in a stretching zone of a tenter stretching machine, uneven thickness in the width direction can be further improved.
- Means for drying the web is not particularly limited, which may generally be hot air, infrared, heating roll, micro wave and the like, of which hot air is preferable in terms of ease.
- the drying step it is effective when the web is heat-treated at drying temperature not more than 5° C. below a glass transition temperature of the film and not less than 100° C. for from 10 or more to 60 or less minutes.
- the drying temperature is 100° C. to 200° C., and more preferably 110° C. to 160° C.
- the knurling may be formed by pressing a heated embossing roll against the film.
- the embossing roll has fine asperities, and asperities are formed on the film by pressing the embossing roll against the film, which can make the ends bulky.
- the knurling on both width ends of the base film of the present invention has a height of 4 to 20 ⁇ m and a width of 5 to 20 mm.
- the above-described knurling is provided after the drying and before the winding in the film manufacturing steps.
- the base film of the present invention has a haze of preferably less than 1%, and more preferably less than 0.5%. With the haze of less than 1%, it is advantageous that the film has improved transparency to be more useful as optical films.
- the base film of the present invention has an equilibrium moisture content under 25° C. and 60% relative humidity of preferably 4% or less, and more preferably 3% or less. With the average moisture content of 4% or less, it is advantageous that tolerance to temperature change is improved and optical characteristics and dimensions are less changeable.
- the base film of the present invention has a thickness of 30 to 100 ⁇ m.
- the thickness is 30 ⁇ m or more, it is advantageous that the web-shaped film is easily handled in manufacturing the film.
- the base film of the present invention has long length. Specifically, the base film is preferably 100 to 10,000 m long, and is winded into a roll shape. Further, the base film of the present invention has a width of preferably 1 m or more, more preferably 1.4 m or more, and particularly 1.4 to 4 m.
- the hard coat layer is provided in contact with the adhesion improver containing resin layer.
- the hard coat layer is preferably a clear hard coat layer or anti-glare hard coat layer.
- an anti-reflection layer which includes at least a low refractive index layer is provided on the hard coat layer in order to improve visibility.
- the hard coat layer of the present invention is a clear hard coat layer
- the hard coat layer has a center line average roughness (Ra) defined in JIS B 0601 of 0.001 to 0.1 ⁇ m.
- the Ra is preferably 0.002 to 0.05 ⁇ m.
- center line average roughness (Ra) is measured with an optical interferotype surface roughness tester.
- Ra may be measured with a non-contact surface micro-profiler WYKO NT-2000 by WYKO Corp.
- the hard coat layer of the present invention When the hard coat layer of the present invention is of anti-glare type, the hard coat layer has fine asperities on the surface. These fine asperities are formed by adding fine particles to the hard coat layer. For example, they may be formed by adding below-mentioned fine particles having an average particle size of 0.01 to 4 ⁇ m to the hard coat layer. Further, as described below, it is preferable that the topmost surface of the anti-reflection layer, which is provided on the anti-glare hard coat layer, has a center line average surface roughness (Ra) defined in JIS B 0601 within a range of 0.08 to 0.5 ⁇ m.
- Ra center line average surface roughness
- the particles which are contained in the hard coat layer of the present invention may be, for example, inorganic or organic fine particles.
- inorganic fine particles examples include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate and the like.
- examples of the organic particles include polymethacrylic acid methylacrylate resin fine particles, acrylic styrene-based resin fine particles, polymethylmethacrylate resin fine particles, silicone-based resin fine particles, polystyrene-based resin fine particles, polycarbonate resin fine particles, benzoguanamine-based resin fine particles, melamine-based resin fine particles, polyolefin-based resin fine particles, polyester-based resin fine particles, polyamide-based resin fine particles, polyimide-based resin fine particles, polyfluoroethylene-based resin fine particles and the like.
- silicon oxide fine particles and polystyrene-based resin fine particles are particularly preferable.
- the above-described inorganic and organic fine particles are added to the application composition which includes resins for manufacturing the anti-glare hard coat layer.
- the organic or inorganic fine particles are blended in an amount of preferably 0.1 to 30 parts by mass, more preferably 0.1 to parts by mass with respect to 100 parts by mass of the resin for the anti-glare hard coat layer.
- fine particles having an average particle size of 0.1 to 1 ⁇ m in an amount of 1 to 15 parts by mass with respect to 100 parts by mass of the resin for the anti-glare hard coat layer it is also preferable to use two or more types of fine particles having different average particle sizes.
- an antistat is contained in the hard coat layer of the present invention.
- the antistat preferably contains at, least one element selected from the group consisting of Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W and V as the main component, as well as is a conductive material having a volume resistivity of 10 7 ⁇ cm or less.
- antistat examples include metal oxides and complex oxides which contain any of the above elements.
- the metal oxides include ZnO, TiO 2 , SnO 2 , Al 2 O 3 , In 2 O 3 , SiO 2 , MgO, BaO, MoO 2 , V 2 O 5 and the like and complex oxides thereof, of which ZnO, In 2 O 3 , TiO 2 and SnO 2 are particularly preferable.
- a heterogeneous atom for example, it is effective to add ZnO with Al, In or the like, TiO 2 with Nb, Ta or the like, and SnO 2 with Sb, Nb, halogen element or the like.
- Such heterogeneous atoms are added in an amount of preferably 0.01 to 25 mol %, and particularly 0.1 to 15 mol.
- These conductive metal oxide powders have a volume resistivity of 10 7 ⁇ cm or less, and particularly 10 7 ⁇ cm or less.
- the clear hard coat layer or anti-glare hard coat layer has a thickness in a range of preferably 0.5 to 15 ⁇ m, and more preferably 1.0 to 7 ⁇ m.
- the hard coat layer of the present invention contains an active ray curing resin which is cured by active ray irradiation such as ultraviolet ray.
- Active energy ray curing resins are curable by cross-linking reaction or the like in response to active energy ray irradiation such as ultraviolet ray or electron beam.
- active energy ray curing resin include ultraviolet curing resins, electron beam curing resins and the like, and may also include other resins which are cured by active energy ray irradiation besides ultraviolet ray and electron beam.
- ultraviolet curing resins examples include, for example, ultraviolet curing acrylic urethane-based resins, ultraviolet curing polyester acrylate-based resins, ultraviolet curing epoxy acrylate-based resins, ultraviolet curing polyol acrylate-based resins, ultraviolet curing epoxy resins and the like.
- ultraviolet curing acrylic urethane resins can be obtained easily by such a way that a polyester polyol is reacted with isocyanate monomer or prepolymer, and the obtained product is further reacted with acrylate-based monomer having a hydroxy (hydroxyl) group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter, “acrylate” is defined to include methacrylate, and only acrylates will be described) or 2-hydroxypropyl acrylate.
- hydroxy (hydroxyl) group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter, “acrylate” is defined to include methacrylate, and only acrylates will be described) or 2-hydroxypropyl acrylate.
- preferably used is a mixture of 100 parts by mass of UNIDIC 17-806 (DIC Corp.) and 1 part by mass of CORONATE L (Nippon Polyurethane Co., Ltd.) and the like, which is described in Japanese Patent Application Laid-Open Publication No. Sho59-151110.
- ultraviolet curing polyester acrylate-based resins can be obtained easily by such a way that a terminal hydroxy (hydroxyl) or carboxyl group of a polyester is reacted with monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate or acrylic acid (see, Japanese Patent Application Laid-Open Publication No. Sho59-151112).
- Ultraviolet curing epoxy acrylate-based resins are obtained by such a way that a terminal hydroxy (hydroxyl) group of an epoxy resin is reacted with monomer such as acrylic acid, acrylic acid chloride or glycidyl acrylate.
- ultraviolet curing polyol acrylate-based resins examples include ethyleneglycol (meth)acrylate, polyethyleneglycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentacrylate and the like.
- Useful active energy ray-reactive epoxy compounds are shown as examples of the ultraviolet curing epoxy acrylate-based resins and ultraviolet curing epoxy resins.
- (e) compounds having an alicyclic epoxide for example, bis(3,4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-cyclohexylmethyl)adipate, bis(3,4-epoxycyclohexylmethyl pimelate) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3′,4′-epoxy-1-methylcyclohexane carboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3′,4′-epoxy-6′-methyl-1′-cyclohexane carboxylate and 2-(3,4-ep
- diglycidyl ethers of glycols for example, ethyleneglycol diglycidylether, diethyleneglycol diglycidylether, propyleneglycol diglycidylether, polyethyleneglycol diglycidylether, polypropyleneglycol diglycidylether, copoly(ethyleneglycol-propyleneglycol)diglycidylether, 1,4-butanediol diglycidylether and 1,6-hexanediol diglycidylether;
- glycidyl esters of polymer acids for example, polyacrylic acid polyglycidylester and polyester diglycidylester;
- glycidyl ethers of polyols for example, glycerin triglycidylether, trimethylolpropane triglycidylether, pentaerythritol diglycidylether, pentaerythritol triglycidylether, pentaerythritol tetraglycidylether and glucose triglycidylether;
- (k) glycidyl ethers of fluorine-containing alkane-terminated diols such as the examples of the fluorine-containing epoxy compounds of the fluororesins as for the above-described low refraction index substances can be given as examples.
- the molecular weight of the above epoxy compounds is 2,000 or less, preferably 1,000 or less by the average molecular weight.
- Photopolymerization initiators or photosensitizers which allow active energy ray reactive epoxy compounds to polymerize by cationic polymerization are compounds which can release a cationic polymerization intiator in response to active energy ray irradiation.
- Particularly preferred are a series of double salts in the form of onium salt which releases aizis acid capable of initiating cationic polymerization in response to irradiation.
- the active energy ray reactive epoxy resins form cross-linked structure or network not by radical polymerization but by cationic polymerization. Such active energy ray reactive resins are preferable because they are not affected by oxygen in the reaction system unlike radical polymerization.
- the active energy ray reactive epoxy resins which are useful for the present invention are polymerized by a photopolymerization initiator or photosenstizer which releases a substance initiating cationic polymerization in response to active energy ray irradiation.
- a photopolymerization initiator or photosenstizer which releases a substance initiating cationic polymerization in response to active energy ray irradiation.
- Particularly preferred photopolymerization initiators are a series of double salts in the form of onium salt which releases aizis acid capable of initiating cationic polymerization in response to irradiation.
- the cation is an onium
- Z is S, Se, Te, P, As, Sb, Bi, O, halogen (e.g., I, Br and Cl) or N ⁇ N (diazo)
- R 1 , R 3 , R 3 and R 4 are organic groups which may be the same or different.
- the notes a, b, c and d are each an integer of 0 to 3, and a+b+c+d is equal to the valence number of Z.
- Me is a metal or metalloid which is a central atom of a halide complex, such as B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn and Co.
- X is a halogen atom
- w is a net electron charge of the halide complex ion
- v is the number of halogen atoms in the halide complex ion.
- anion [MeX v ] w ⁇ of the above general formula (c) include tetrafluoroborate (BF 4 ⁇ ), tetrafluorophosphoate (PF 1 ⁇ ), tetrafluoroantimonate (SbF 4 ⁇ ), tetrafluoroarsenate (AsF 4 ⁇ ), tetrachloroantimonate (SbCl 4 ⁇ ) and the like.
- anionic ion examples include perchlorate ion (ClO 4 ⁇ ), trifluoromethylsulfite ion (CF 3 SO 3 ⁇ ), fluorosulfonate ion (FSO 3 ⁇ ), toluene sulfonate ion, trinitrobenzoate anion and the like.
- aromatic onium salts it is particularly effective to use aromatic onium salts as the cationic polymerization initiator.
- aromatic onium salts preferred are aromatic halonium salts described in Japanese Patent Application Laid-Open Publication Nos. Sho50-151996, Sho50-158680 and the like, group VIA salts of aromatic onium salts described in Japanese Patent Application Laid-Open Publication Nos. Sho50-151997, Sho52-30899, Sho59-55420, Sho55-125105 and the like, oxosulfoxonium salts described in Japanese Patent Application Laid-Open Publication Nos.
- a photosenstizer may be n-butyl amine, tryethylamine, tri-n-butylphosphine and the like.
- a sufficient amount for initiating photoreaction is 0.1 to 15 parts by mass, and preferably 1 to 10 parts by mass with respect to 100 parts by mass of the ultraviolet reactive compound. It is preferable that this sensitizer has an absorption maximum within the range of near-ultraviolet to visible light.
- the polymerization initiator is generally used in an amount of preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the active energy ray curing epoxy resin (prepolymer).
- the epoxy resin may be used in combination with the above-described urethane acrylate-type resin, polyether acrylate-type resin or the like.
- an active energy ray radical polymerization initiator in combination with an active energy ray cationic polymerization initiator.
- an oxetane compound may be used.
- Employable oxetane compounds have a three-membered oxetane ring including oxygen or sulfur.
- compounds having an oxygen-including oxetane ring are preferable.
- the oxetane ring may be substituted with a halogen atom, haloalkyl group, arylalkyl group, alkoxyl group, allyloxy group or acetoxy group.
- the above-described active energy ray curing resin may be mixed with a binder such as known thermoplastic resins, thermosetting resins and hydrophilic resins like gelatin. These resins preferably have a polar group in the molecule.
- the polar group include —COOM, —OH, —NR 2 , —NR 3 X, —SO 3 M, —OSO 3 M, —PO 3 M 2 , —OPO 3 M (where M represents a hydrogen atom, alkali metal or ammonium group, X represents an acid constituting an amine salt, R represents a hydrogen atom or alkyl group) and the like.
- active energy ray irradiation may be performed after the hard coat layer, anti-reflection layer (middle to high refractive index layer and low refractive index layer) and the like are applied onto the support.
- the irradiation is preferably performed in applying the hard coat layer.
- the active energy ray used in the present invention is ultraviolet ray, electron beam, ⁇ ray or the like, and is not limited as long as it is an energy source capable of activating the compound.
- ultraviolet ray and electron beam are preferable.
- Ultraviolet ray is particularly preferable because it is easy to handle and high energy can easily be obtained.
- a light source of the ultraviolet ray which photo-polymerizes the ultraviolet reactive compound may be any light source as long as it generates ultraviolet ray.
- a low-pressure mercury lamp, middle-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, carbon arc lamp, metalhalide lamp or xenon lamp may be used.
- an Ar—F excimer laser, Kr—F excimer laser, excimer lamp, synchrotron radiation or the like may also be used. It is preferable to use a light source which has an emission spectrum in an ultraviolet region of 250 to 420 nm wavelength. Although irradiation conditions vary depending on types of lamps, irradiation dose is preferably 20 mJ/cm 2 or more, more preferably 50 to 2,000 mJ/cm 2 , and particularly 50 to 1,000 mJ/cm 2 .
- the ultraviolet irradiation may be performed on the hard coat layer and a plurality of layers (middle refractive index layer, high refractive index layer and low refractive index layer) constituting the anti-reflection layer every time a single layer is formed, or may be performed after the layers are overlayed. Alternatively, the irradiation may be performed by the above ways in combination. In terms of productivity, it is preferable that the ultraviolet irradiation is performed after the plurality of layers are overlayed.
- electron beam may be used in the same manner.
- the electron beam may be emitted from various types of electron beam accelerators such as Cockcroft-Walton type, Van de Graaff type, resonance transformer type, insulated core transformer type, linear type, dynamitron type and high-frequency type accelerators, with an energy of 50 to 1,000 keV, and preferably 100 to 300 keV.
- electron beam accelerators such as Cockcroft-Walton type, Van de Graaff type, resonance transformer type, insulated core transformer type, linear type, dynamitron type and high-frequency type accelerators, with an energy of 50 to 1,000 keV, and preferably 100 to 300 keV.
- the above-described active energy ray reactive compound which is used in the present invention can initiate the photopolymerization or photocross-linking reaction by itself. However, because the introduction period is long or the polymerization starts late, it is preferable to use a photosensitizer or photoinitiator, which can accelerate the polymerization.
- the hard coat layer of the present invention contains the active energy ray curing resin
- the active energy ray may be irradiated in the presence of the photoreactive initiator and photosensitizer.
- acetophenone benzophenone, hydroxybenzophenone, Michler's ketone, ⁇ -amyloxime ester, thioxanthone and derivatives thereof.
- a photoreactive agent such as n-butylamine, triethylamine and tri-n-buthylphosphine may be used.
- the photoreactive initiator and/or photosensitizer is used in an amount of preferably 1 to 10 mass %, and particularly 2.5 to 6 mass % of the ultraviolet curing resin composition excluding the solvent component which volatilizes after applied and dried.
- an ultraviolet absorber described below may be contained in the ultraviolet curing resin composition to the extent not inhibiting the ultraviolet curing resin from photocuring.
- an antioxidant which does not inhibit photocuring reaction may be selected and used.
- examples include, for example, hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives and the like.
- Specific examples include, for example, 4,4′-thiobis(6-tert-3-methylphenol), 4,4′-butylidene-bis(6-tert-butyl-3-methylphenol), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)mesitylene, di-octadecyl-4-hydroxy-3,5-di-tert-butylbenzylphosphate and the like.
- the ultraviolet curing resin may be selected from, for example, ADEKAOPTOMER KR and BY series, i.e., KR-400, KR-410, KR-550, KR-566, KR-567 and BY-320B (ADEKA Corp.), KOEIHARD A-101-KK, A-101-WS, C-302, C-401-N, C-50, M-10, M-102, T-102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106 and M-101-C (Koei Chemical formulaical Co.
- KR-400 KR-400, KR-410, KR-550, KR-566, KR-567 and BY-320B
- KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL 29201 and UVECRYL 29202 (Daicel UCB Corp.), RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180 and RC-5181 (DIC Corp.), OLEX No. 340 clear (Chugoku Marine.
- the application composition containing the active energy ray curing resin has a solid component concentration of 10 to 95 mass %, and a suitable concentration is selected according to an application method.
- the hard coat layer of the present invention contains a surfactant, and preferable surfactants are silicone-based surfactants or fluorosurfactants.
- silicone-based surfactants are nonionic surfactants which have methylpolysiloxane as a hydrophobic group and polyoxyalkylene as a hydrophilic group.
- Nonionic surfactants are a general term for surfactants having no group which dissociates to produce ion in aqueous solution, and have hydroxy (hydroxyl) groups of polyol or a polyoxyalkylene chain (polyoxyehylene) as a hydrophilic group as well as a hydrophobic group.
- hydroxy (hydroxyl) groups of polyol or a polyoxyalkylene chain polyoxyehylene
- the nonionic surfactants of the present invention are characterized by having dimethylpolysiloxane as the hydrophobic group.
- nonionic surfactant which have methylpolysiloxane the hydrophobic group and polyoxyalkylene the hydrophilic group, unevenness of the anti-glare hard coat layer and low refractive index layer and antifouling characteristics of the film surfaces are improved. It is supposed that the polymethylsiloxane hydrophobic groups are oriented on the surface to form an anti-fouling film surface. This advantage cannot be obtained by use of the other surfactants.
- nonionic surfactants include, for example, silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164, FZ-2166 and FZ-2191 produced by Nippon Unicar Co., Ltd. and the like.
- silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164, FZ-2166 and FZ-2191 produced
- SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805 can also be given as examples.
- the surfactant is such a linear block copolymer that dimethylpolysiloxane structural moieties and polyoxyalkylene chains are alternately linked to each other.
- Such structure is excellent because a main chain backbone is long and linear. It is supposed that because hydrophilic and hydrophobic groups are alternately repeated in the block copolymer, one active agent molecule traps a silica fine particle at a plurality of sites on the surface so as to cover the particle.
- silicone surfactants ABN SILWET FZ-2203, FZ-2207 and FZ-2208 produced by Nippon Unicar Co., Ltd. and the like.
- the fluorosurfactants may be surfactants in which the hydrophobic group has a perfluorocarbon chain.
- Such surfactants include fluoroalkyl carboxylic acid, disodium N-perfluorooctane sulfonyl glutaminate, sodium 3-(fluoroalkyloxy)-1-alkylsulfate, sodium 3-(o-fluoroalkanoyl-N-ethylamino)-1-propanesulfonate, N-(3-perfluorooctane sulfoneamide) propyl-N,N-dimethyl-N-carboxymethylene ammoniumbetaine, perfluoroalkyl carboxylic acid, perfluorooctane sulfonic acid diethanolamide, perfluoroalkylsulfonate, N-propyl-N-(2-hydroxyethyl)perfluorooctane sulfoneamide, perfluoroalky
- fluorosurfactants are commercially available in the product names of MEGAFAC, EFTOP, SURFLON, FTERGENT, UNIDYNE, FLUORAD, ZONYL and the like.
- the amount to be added is preferably 0.01% to 3.0%, and more preferably 0.02% to 1.0% with respect to the solid component of the hard coat layer application liquid.
- surfactants may be suitably used together.
- sulfonate-based, sulfate-based and phosphate-based anionic surfactants, ether and etherester nonionic surfactants which have a polyoxyethylene chain as the hydrophilic group and the like may be suitably used together.
- the solvent which is used for applying the hard coat layer of the present invention may be suitably selected from, for example, hydrocarbon atoms, alcohols, ketones, esters, glycolethers and other solvents, or combinations thereof.
- solvents which contain 5 mass % or more of propyleneglycol mono(C1-C4)alkylether or propyleneglycol mono (C1-C4) alkyletherester and more preferably 5 to 80 mass % or more.
- the hard coat layer composition application liquid may be applied using any known method such as gravure coating, spinner coating, wire bar coating, roll coating, reverse coating, extrusion coating, air doctor coating, spray coating or inkjet.
- Suitable application amount is 5 to 30 ⁇ m in wet film thickness, and preferably 10 to 20 ⁇ m.
- the application rate is preferably 10 to 200 r/min.
- the hard coat layer composition is preferably cured by active energy ray irradiation such as ultraviolet ray or electron beam.
- Irradiation time of the active energy ray is preferably 0.5 sec to 5 min, and more preferably 3 sec to 2 min considering the curing efficiency of the ultraviolet curing resin, work efficiency and the like.
- an anti-reflection layer on the hard coat layer is provided on the hard coat layer of the base film.
- the anti-reflection layer to be used may be composed of only a single low refractive index layer.
- the anti-reflection layer is composed of a plurality of refractive index layers.
- the anti-reflection layer may be further overlayed on the surface where the adhesion improver containing resin layer and hard coat layer are provided on the base film, so as to reduce the reflectance by optical interference considering refractive index, film thickness, the number of layers, order of layers and the like.
- the anti-reflection layer may be composed of a high refractive index layer having a refractive index higher than a refractive index of the support and a low refractive index layer having a refractive index lower than a refractive index of the support.
- the anti-reflection layer is composed of three or more refractive index layers. It is preferable that three layers having different refractive indexes are overlayed in the order, from the support side, of middle refractive index layer (having a refractive index higher than reflective indexes of the support and anti-glare hard coat layer but lower than a reflective index of the high refractive index layer)/high refractive index layer/low refractive index layer.
- the anti-reflection layer is composed of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately overlayed.
- base film/adhesion improver containing resin layer/clear hard coat layer/middle refractive index layer/high refractive index layer/low refractive index layer;
- base film/adhesion improver containing resin layer/anti-glare hard coat layer/middle refractive index layer/high refractive index layer/low refractive index layer.
- An antifouling layer may be further provided on the topmost low refractive index layer so as to make it easy to wipe out smudges and fingerprints.
- a fluoroorganic compound is preferably used for the antifouling layer.
- the layer configuration is not limited to the above examples as long as the reflectance can be reduced by optical interference.
- a suitable intermediate layer may be further provided, a preferable example of which is, for example, an antistat layer which contains conductive polymer fine particles (e.g., cross-linked cation fine particles) or metal oxide fine particles (e.g., SnO 2 , ITO and the like), and the like.
- the low refractive index layer, middle refractive index layer and high refractive index layer may be formed in any known configurations.
- hollow spherical silica-based fine particles are suitably used in the low refractive index layer, which particles may be (I) complex particles composed of porous particles and coating layers provided on the surfaces of the porous particles, or (II) hollow particles having hollows filled with solvent, gas or porous substance.
- each refractive index layer of the anti-reflection layer is preferably in a range of 1 to 200 nm, and more preferably 5 to 150 nm. It is preferable to choose a suitable thickness according to the refractive index of each layer.
- the anti-reflection layer which is used in the present invention has an average reflectance in 450 to 650 nm of 1% or less, and particularly 0.5% or less. Further, it is particularly preferable that the minimum reflectance in this range is 0.00 to 0.3%.
- the refractive index and film thickness of the anti-reflection layer can be calculated from a measuring result of the spectral reflectance. Further, optical reflection characteristics of a produced low reflection film can be determined by measuring specular reflectance at 5° by use of a spectorophotometer.
- Cellulose acylates having acetyl substitution degrees shown in Table 1 were synthesized by the methods described in Japanese Patent Application Laid-Open Publication Nos. Hei10-45804 and Hei08-231761, and the substitution degrees were measured. Specifically, sulfuric acid (7.8 parts by mass with respect to 100 parts by mass of cellulose) was added as a catalyst, and carboxylic acid was added as the raw material of acethyl substitutents. Then, acylation reaction was initiated at 40° C. At this time, types and amount of the carboxylic acid were adjusted so as to control the substitution degree. Further, aging was performed at 40° C. after the acylation. Furthermore, the low molecular weight components of the cellulose acylates were removed by washing with acetone.
- substitution degrees were determined by the measurement defined in ASTM-D817-96.
- a cellulose acylate referred to as CAP is cellulose acetatepropionate (acetyl substitution degree of 1.90, propionyl substitution degree of 0.54).
- M-1 TINUVIN 928 ( ⁇ max of 348 nm, BASF Japan Ltd.)
- M-2 TINUVIN 326 ( ⁇ max of 353 nm, BASF Japan. Ltd.)
- M-3 TINUVIN 571 ( ⁇ max of 344 nm, BASF Japan Ltd.
- Absorption maximum peak ( ⁇ max) was measured with solutions where the above compounds dissolved in solvent (dichloromethane or toluene) by use of a spectrophotometer UVIDFC-610 produced by Shimadzu Corp. As a result, it was confirmed that every compound had the absorption maximum peak ( ⁇ max) within the range of 260 to 400 nm.
- Fine particles (AEROSIL R812, Nippon Aerosil Co., Ltd.): 11 parts by mass
- the fine particle dispersion 1 was gradually added to methylene chloride in a melting furnace under thorough stirring. The mixture was further dispersed by use of an attritor so as to adjust the secondary particles size to a predetermined value. The product was filtrated with a FINEMET NF produced by NipponSeisen Co., Ltd. Fine particle added solution 1 was thus prepared.
- Fine particle dispersion 1 5 parts by mass
- a main dope solution having the following composition was prepared. First, methylene chloride and ethanol was placed in a pressure dissolution tank. Into the pressure dissolution tank with the solvents, cellulose acetate having an acetyl substitution degree of 2.88 was added under stirring. This mixture was heated under stirring for thorough dissolution. This solution was filtrated with an AZUMI filter paper No. 244 produced by Azumi Filter Paper Co., Ltd. The main dope solution was thus prepared.
- Cellulose acetate (acetyl substitution degree of 2.88, weight average molecular weight of 140,000): 100 parts by mass
- Triphenylene phosphate 12 parts by mass
- Biphenyldiphenyl phosphate 6 parts by mass
- Tribenzylamine 2 parts by mass
- Fine particle added solution 1:1 part by mass
- the above materials were placed into a sealed main dissolution furnace and dissolved under stirring.
- the dope solution was thus prepared.
- the solvent in a casted film was allowed to volatilize until the residual solvent amount decreased down to 75%, and then the film was stripped from the stainless steel belt support by a stripping tensile force of 130 N/m.
- the stripped cellulose acylate film was stretched by 20% in the width direction using a tenter with heat at 170° C. The residual solvent was 15% at the start of the stretching.
- the film was conveyed through a dry zone with a plurality of rolls so as to complete the drying.
- the drying temperature was 130° C. and the conveying tension was 100N/m. Accordingly, a cellulose acylate film 101 having a dry film thickness of 40 ⁇ m was obtained.
- cellulose acylate films 102 and 103 were prepared in the same manner except that the CAP and cellulose acylate having an acetyl substitution degree of 2.43 were used.
- the following three types of dope were prepared, and a laminated cellulose acylate film 104 having a core and skin portions was prepared by co-film casting.
- Cellulose acetate (acetyl substitution degree of 2.43, weight average molecular weight of 210,000): 100 parts by mass
- Triphenylene phosphate 20 parts by mass
- Cellulose acetate (acetyl substitution degree of 2.88, weight average molecular weight of 140,000): 100 parts by mass
- Triphenylene phosphate 12 parts by mass
- Biphenyldiphenyl phosphate 6 parts by mass
- Tribenzylamine 2 parts by mass
- Fine particle added solution 1:1 part by mass
- Cellulose acetate (acetyl substitution degree of 2.88, weight average molecular weight of 140,000): 100 parts by mass
- Triphenylene phosphate 20 parts by mass
- Fine particle added solution 1:1 part by mass
- each of the above compositions was placed in a mixing tank. After stirred to dissolve the components, each of the solution was filtrated with a filter paper having an average pore size of 34 ⁇ m and with a sintered metal filter having an average pore size of 10 ⁇ m.
- the cellulose acylate dopes were thus prepared.
- the dopes were co-casted with a band film casting machine so as to obtain three-layered structure of hard coat skin layer on hard coat layer side/core layer/skin layer.
- the simultaneous multilayer film casting was performed adjusting the casting amount of each dope in order that the core layer was the thickest layer and the film thicknesses after stretching were 2 ⁇ m/45 ⁇ m/2 ⁇ m.
- the film which was stripped from a band when the residual solvent amount was about 30 mass %, was stretched widthwise by a stretching ratio of 32% using a tenter while being blown with hot air of 140° C., and then relaxed at 140° C. for 60 sec so as to adjust the stretching ratio to 30%.
- the film was then transferred from the tenter conveyor to a roll conveyor, and further dried at 120° C. to 150° C. and winded.
- tungsten hexachloride (0.7% toluene solution) and a norbornene-based monomer mixture which was composed of 20 parts by mass of tricyclo[4.3.0.12,5]deca-3,7-diene (dicyclopentadiene, hereinafter abbreviated as DCP)
- DCP dicyclopentadiene
- MTF 1,4-methano-1,4,4a,9a-tetrahydrofluorene
- MTD 8-methyl-tetracyclo[4.4.0.12, 5.17,10]-dodeca-3-ene
- reaction solution containing 20% of a hydrogenated DCP/MTF/MTD ring-opening polymer product.
- This hydrogenated ring-opening polymerization product had a weight average molecular weight (Mw) of 31,000, molecular weight distribution (Mw/Mn) of 2.5, hydrogenation degree of 99.9% and Tg of 134° C.
- the obtained pellets of the hydrogenated ring-opening polymerization product were dried at 70° C. for 2 hours to remove water by use of an air-circulating hot air dryer.
- the pellets were melt-extruded into a cycloolefin film 105 of 80 ⁇ m thick by use of a short axis extruder equipped with a coat-hanger T-die of 1.6 m lip width (Mitsubishi Heavy Industries, Ltd., screw size of 90 mm, T-die lip of tungsten carbide, peel strength of melted resin of 44 N).
- the extrusion molding was performed in a cleanroom of class 20,000 or less in the molding condition of a melted resin temperature of 240° C. and T-die temperature of 240° C.
- the obtained cycloolefin resin film 105 was slitted to remove both edges, and thus shaped into 1.5 m width. Further, a polyester film was winded together as a protective film.
- an adhesion improver containing resin layer was applied onto the surface of the cellulose acylate film 101 so that the dry film thickness was about 0.2 ⁇ m, and dried in a dry section at 80° C.
- Polymethyl methacrylate (weight average molecular weight of 30,000): 100 parts by mass
- Methylethylketone 6000 parts by mass
- Adhesion improver M-1 0.1 part by mass
- Pentaerythritol triacrylate 30 parts by mass
- Pentaerythritol tetraacrylate 45 parts by mass
- Urethane acrylate product name of U-4HA, Shin-Nakamura Chemical formulaical Co., Ltd.: 25 parts by mass 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184, BASF Japan, Ltd.): 5 parts by mass 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-one: (IRGACURE 907, BASF Japan, Ltd.): 3 parts by mass
- BYK-331 silicone surfactant, BYK Japan Corp.: 0.5 part by mass
- Application liquids were prepared in the same manner as the adhesion improver containing resin layer application liquid 1 except that the type of adhesion improver and the content thereof were changed. These application liquids were applied onto the base films shown in Table 1 so that the dry film was about 0.2 ⁇ m, and dried in a drying section at 80° C.
- Hard coat layers 202 to 225 were thus prepared.
- the hard coat films 223 to 225 were directly formed onto the base films without providing the adhesion improver containing resin layer.
- liquid crystal display devices with front plates 202 to 225 were prepared in the same manner.
- the base films where the adhesion improver containing resin layers as prepared above were provided were subjected to the measurement of light transmittance at 380 nm by use of a spectrophotometer UVIDFC-610 produced by Shimadzu Corp.
- ⁇ light transmittance at 380 nm was 51% or more to less than 70%
- the devices were subjected to a cross-cut adhesion test so as to evaluate the adhesiveness of the hard coat layers of the hard coat films. Specifically, a test area was set to 1 cm square. One-mm grid incision was made on the surface of the hard coat layer with such a depth that the incision barely reached the surface of transparent plastic film by use of a single-edged razor blade. Commercially-available 25-mm width cellophane tape was stuck on the hard coat layer in such a manner that one end of the tape was left unattached.
- the tape was rubbed so as to be adhered well, and then peeled by pulling the unattached end of the tape strongly by a hand in a perpendicular direction.
- the proportion of the area where the hard coat layer was peeled with respect to the taped area was determined based on the incision, and was evaluated as follows. If the peeled area is 1.5% or more of the tested area, the practicality is low.
- the peeled area was 15% or more to less than 30% of the tested area
- the peeled area was 30% or more of the tested area.
- the on-axis contrast was measured at arbitrary 10 points on each liquid display device, and evaluated according to the following criteria.
- Uneven contrast may be caused by wrinkles or distortion of a hard coat film as well as by a defectively cured sealing layer.
- ⁇ on-axis contrast variation was 1% to less than 5%, i.e., small unevenness
- ⁇ on-axis contrast variation was 5% to less than 10%, i.e., moderate unevenness
- On-axis contrast variation was 10% or more, i.r., large unevenness.
- each of the liquid crystal display devices with front plates in which the base film having the adhesion improver containing resin layer of the present invention and the hard coat layer is pasted on the front plate had low haze and were excellent in contrast uniformity and adhesiveness between the hard coat layer and the base film compared to the comparative liquid crystal display devices with front plates.
- the following dope was prepared, and a cellulose acylate film 301 was prepared in the same manner as the first embodiment.
- Cellulose acetate (acetyl substitution degree of 2.88, weight average molecular weight or 140,000): 100 parts by mass
- Triphenylene phosphate 12 parts by mass
- polyester (P) 5 parts by mass
- Fine particles additive solution 1:1 part by mass
- the above materials were placed into a main dissolution furnace 1, and dissolved under stirring to prepare a dope solution.
- the solvent in a casted film was allowed to volatilize until the residual solvent amount decreased down to 75%, and subsequently the film was stripped from the stainless steel belt support by a stripping tensile force of 130 N/m.
- the stripped cellulose acylate film was stretched by 10% in the width direction using a tenter with heat at 170° C. The residual solvent was 15% at the start of the stretching.
- the film was stretched by 10% also in the longitudinal direction.
- the film was conveyed through a dry zone with a plurality of rolls to complete the drying.
- the drying temperature was 130° C. and the conveying tension was 100 N/m. Accordingly, a cellulose acylate film 301 having a dry film thickness of 40 ⁇ m was obtained.
- cellulose acylate films 302 to 305 were prepared in the same manner except that the film thickness was changed as shown in Table 2.
- PET film polyethylene terephthalate film
- Liquid crystal display devices with front plates 401 to 407 were prepared in the same manner as the first embodiment using the hard coat films 401 to 405 and the hard coat film 201 which was prepared in the first embodiment and polyethylene terephthalate film (PET film), respectively.
- PET film polyethylene terephthalate film
- the prepared cellulose acylate films 101 , 301 to 305 and polyethylene terephthalate film (PET film) were subjected to the measurement of retardations Ro and Rth according to the following method.
- the average refractive index of each film sample was measured by use of an Abbe refractometer and spectroscopic light source, and the film thickness was measured by use of a commercially available micrometer.
- nx, ny and nz are refractive indexes in the condition of 23° C., 55% RH and 590 nm, where nx represents the maximum refractive index in the film plane (also called refractive index in the slow axis direction); ny represents the refractive index in the direction perpendicular to the slow axis in the film plane; nz represents the refractive index of the film in the thickness direction; and d is the film thickness (nm).
- the adhesiveness between the hard coat layer and cellulose acylate film was evaluated in the same manner as the first embodiment.
- 3D glasses TDG-BR100 produced by Sony was used.
- the hard coat films 401 to 405 and 201 which are provided with the adhesion improver containing resin layer of the present invention, were excellent in the adhesiveness between the hard coat layer and the cellulose acylate film. Furthermore, the hard coat films 401 to 405 had low retardations Ro and Rth. Therefore, it was found that the liquid display devices with front plates which were provided with such hard coat films had small crosstalk of 3D images, and excellent liquid crystal display devices for stereoscopic image can be provided.
- the liquid crystal display device 407 which had a front plate of PET film had moire and was inferior in display qualities. Further, it was also found that the crosstalk of 3D images was too large for practical use.
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Abstract
Description
- Patent literature 1: Japanese Patent Application Laid-Open Publication No. 2003-107433
Ro=(nx−ny)×d equation (i)
Rth={(nx+ny)/2−nz}×d equation (ii)
Ro=(nx−ny)×d Equation (i)
Rth={(nx+ny)/2−nz}×d Equation (ii)
1.5≦X+Y≦2.95 Inequality (I)
1.5≦X≦2.95 Inequality (II)
R11—(OH)n General formula (a)
R12(COOH)m1(OH)n1 General formula (b)
R311—X311—Z311—X312—R312 General formula (7-1)
Residual solvent amount (mass %)={(M−N)/N}×100
[(R1)a(R2)b(R3)c(R4)dZ]w+[MeXv]w− General formula (c)
On-axis contrast=(brightness of white image measured in normal direction of display device)/(brightness of black image measured in normal direction of display device)
TABLE 1 | ||||
Adhesion improver containing | ||||
Hard | resin layer |
coat | Base | Acetyl | Type of | Content of | Adhesiveness | |||
film | film | substitution | adhesion | adhesion improver | Light | of adhesion | Contrast | |
No. | No. | degree | improver | (part by mass) | transmittance | improver | unevenness | Note |
201 | 101 | 2.88 | M-1 | 0.1 | ⊚ | ⊚ | ⊚ | Present invention |
202 | 101 | 2.88 | M-1 | 0.005 | ⊚ | ◯ | ◯ | Present invention |
203 | 101 | 2.88 | M-1 | 0.3 | ⊚ | ⊚ | ⊚ | Present invention |
204 | 101 | 2.88 | M-1 | 0.5 | ⊚ | ⊚ | ⊚ | Present invention |
205 | 101 | 2.88 | M-1 | 0.004 | Δ | X | X | Comparative Example |
206 | 101 | 2.88 | M-1 | 0.6 | Δ | X | X | Comparative Example |
207 | 102 | 2.43 | M-1 | 0.1 | ◯ | ◯ | ◯ | Present invention |
208 | 103 | CAP | M-1 | 0.1 | ◯ | ◯ | ◯ | Present invention |
209 | 104 | 2.88/2.43/2.88 | M-1 | 0.1 | ⊚ | ⊚ | ⊚ | Present invention |
210 | 104 | 2.88/2.43/2.88 | M-1 | 0.5 | ⊚ | ⊚ | ⊚ | Present invention |
211 | 105 | Cycloolefin | M-1 | 0.005 | ◯ | ◯ | ◯ | Present invention |
212 | 105 | Cycloolefin | M-1 | 0.1 | ⊚ | ◯ | ◯ | Present invention |
213 | 105 | Cycloolefin | M-1 | 0.5 | ⊚ | ◯ | ◯ | Present invention |
214 | 105 | Cycloolefin | M-1 | 0.6 | X | X | X | Comparative Example |
215 | 101 | 2.88 | M-2 | 0.1 | ⊚ | ⊚ | ⊚ | Present invention |
216 | 101 | 2.88 | M-2 | 0.3 | ⊚ | ⊚ | ⊚ | Present invention |
217 | 101 | 2.88 | M-2 | 0.5 | ⊚ | ⊚ | ⊚ | Present invention |
218 | 101 | 2.88 | M-3 | 0.1 | ⊚ | ⊚ | ⊚ | Present invention |
219 | 101 | 2.88 | M-3 | 0.3 | ⊚ | ⊚ | ⊚ | Present invention |
220 | 101 | 2.88 | M-3 | 0.5 | ⊚ | ⊚ | ⊚ | Present invention |
221 | 101 | 2.88 | M-4 | 0.1 | ◯ | ◯ | ◯ | Present invention |
222 | 101 | 2.88 | M-4 | 0.3 | ◯ | ◯ | ◯ | Present invention |
223 | 101 | 2.88 | — | — | Δ | X | X | Comparative Example |
224 | 104 | 2.88/2.43/2.88 | — | — | Δ | X | X | Comparative Example |
225 | 105 | Cycloolefin | — | — | Δ | X | X | Comparative Example |
Ro=(nx−ny)×d Equation (i)
Rth={(nx+ny)/2−nz}×d Equation (ii)
TABLE 2 | |||||||
Hard | Total | Cross | |||||
Display | coat | Cellulose | thickness | Adhesiveness | talk in | ||
device | film | acylate | of film | Retardation | of hard coat | 3D |
No. | No. | film No. | (μm) | Ro (nm) | Rth (nm) | layer | display | Note |
401 | 401 | 301 | 40 | 0.7 | 1 | ⊚ | ⊚ | Present invention |
402 | 402 | 302 | 60 | 2 | 5 | ◯ | ◯ | Present invention |
403 | 403 | 303 | 80 | 5 | 10 | ◯ | ◯ | Present invention |
404 | 404 | 304 | 20 | 1 | −3 | ⊚ | ⊚ | Present invention |
405 | 405 | 305 | 30 | 2 | −2 | ⊚ | ⊚ | Present invention |
406 | 201 | 101 | 40 | 5 | 45 | ⊚ | Δ | Present invention |
407 | PET | — | 40 | 3800 | — | — | — | Comparative Example |
film | ||||||||
- 1, 1′ polarizing plate
- 2 liquid crystal cell
- 3 sealing layer
- 4 front plate
- 5 adhesive layer
- 6 cellulose acylate film
- 7 adhesion improver containing resin layer
- 8 hard coat layer
- 10 co-casting die
- 11 mouthpiece
- 13, 15 skin layer-forming slit
- 14 core layer-forming slit
- 16 metal support
- 17, 19 skin layer-forming dope
- 18 core layer-forming dope
- 20 multi-layered web
- 21 skin layer
- 22 core layer
- 23 skin layer
Claims (8)
Ro=(nx−ny)×d expression (i):
Rth={(nx+ny)/2−nz}×d expression (ii):
Applications Claiming Priority (3)
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JP2010-248192 | 2010-11-05 | ||
JP2010248192 | 2010-11-05 | ||
PCT/JP2011/075066 WO2012060324A1 (en) | 2010-11-05 | 2011-10-31 | Method for manufacturing liquid crystal display device provided with front plate, and liquid crystal display device provided with front plate |
Publications (2)
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US20130222720A1 US20130222720A1 (en) | 2013-08-29 |
US9563075B2 true US9563075B2 (en) | 2017-02-07 |
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US13/882,903 Active 2031-11-02 US9563075B2 (en) | 2010-11-05 | 2011-10-31 | Method for manufacturing liquid crystal display device provided with front plate, and liquid crystal display device provided with front plate |
Country Status (3)
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US (1) | US9563075B2 (en) |
JP (1) | JP5678965B2 (en) |
WO (1) | WO2012060324A1 (en) |
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GB2515264A (en) * | 2013-05-03 | 2014-12-24 | Pro Display Tm Ltd | Improved method of forming switchable glass |
WO2015115329A1 (en) * | 2014-01-29 | 2015-08-06 | コニカミノルタ株式会社 | Optical film |
JP6495625B2 (en) * | 2014-11-11 | 2019-04-03 | 株式会社ジャパンディスプレイ | Display device |
KR20160097429A (en) * | 2015-02-06 | 2016-08-18 | 삼성디스플레이 주식회사 | Display device |
JP2016212146A (en) * | 2015-04-30 | 2016-12-15 | コニカミノルタ株式会社 | Optical film and method for manufacturing the same |
US11163132B2 (en) * | 2016-04-18 | 2021-11-02 | Canon Kabushiki Kaisha | Thermal barrier film, thermal barrier paint, and optical instrument |
KR102389846B1 (en) * | 2016-09-30 | 2022-04-21 | 니폰 제온 가부시키가이샤 | Resin film and conductive film, manufacturing method thereof |
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US20030011315A1 (en) * | 2001-06-20 | 2003-01-16 | Dai Nippon Printing Co., Ltd. | Cover plate for display device, method of making the same, display device and reflection-reducing structure |
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JP2003255105A (en) | 2002-03-05 | 2003-09-10 | Fuji Photo Film Co Ltd | Transparent antireflection film, optical filter and image display device |
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- 2011-10-31 US US13/882,903 patent/US9563075B2/en active Active
- 2011-10-31 WO PCT/JP2011/075066 patent/WO2012060324A1/en active Application Filing
- 2011-10-31 JP JP2012541851A patent/JP5678965B2/en active Active
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US20130222720A1 (en) | 2013-08-29 |
JPWO2012060324A1 (en) | 2014-05-12 |
WO2012060324A1 (en) | 2012-05-10 |
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